Herbicides

ABSTRACT

Compounds of formula (I) in which A is ═N— or (a); W is a group (W1), (W2) or (W3); R 11  is hydrogen, fluorine, chlorine, bromine or methyl; and R 1  to R 5 , R 13 ,n 1  and n 13  are as defined in claim 1, and the pyrazole N-oxydes, agrochemically tolerated salts and stereoisomers of these compounds of formula (I), have good pre- and post-emergent selective herbicidal properties. The preparation of these compounds and their use as herbidical active substances are described.

This is a 371 of PCT/EP97/06243 Nov. 10, 1997, now WO98/21199.

The present invention relates to novel herbicidally active substitutedpyrazole derivatives, a process for their preparation, compositionscomprising these compounds and their use for controlling weeds, inparticular in crops of useful plants, for example cereals, maize, rice,cotton, soya, oilseed rape, sorghum, sugarcane, sugarbeet, sunflowers,vegetables, plantations and fodder plants, or for inhibiting plantgrowth. Phenyl-pyrazole compounds having a herbicidal action are knownand are described, for example, in EP-A-0 361 114, U.S. Pat. No.5,032,165, WO 92/02509, WO 92106962, WO 95133728 and WO 96/01254. It hasnow been found, surprisingly, that substituted pyridyl-pyrazolederivatives have outstanding herbicidal and growth-inhibitingproperties.

The present invention therefore relates to compounds of the formula I

in which

A is ═N— or

n₁₃ is 1, 2 or 3;

R₁ is hydrogen, C₁-C₄alkyl, C₁-C₄halogenoalkyl, cyano-C₁-C₄alkyl, C₃- orC₄alkenyl, C₃- or C₄halogenoalkenyl, C₃- or C₄alkynyl orC₃-C₆cycloalkyl;

R₂ is hydrogen, C₁-C₄alkyl, C₁-C₄halogenoalkyl, C₃-C₆alkenyl,C₃-C₆halogenoalkenyl, C₃-C₆alkynyl, C₁-C₄alkylsulfonyl,C₁-C₄halogenoalkylsulfonyl, C₂-C₄alkenylsulfonyl orC₂-C₄halogenoalkenylsulfonyl;

R₃ is hydrogen, C₁-C₄alkyl, C₁-C₄halogenoalkyl, C₁-C₄hydroxyalkyl,C₂-C₆alkenyl, C₂-C₆-halogenoalkenyl, C₂-C₆alkynyl, halogen, cyano,NH₂C(S)—, nitro, OHC— or R₁₈R₁₉N—;

R₁₈ and R₁₉ independently of one another are hydrogen, C₁-C₄alkyl,C₁-C₄halogenoalkyl, C₃-C₄alkenyl, C₃-C₄halogenoalkenyl, C₃-C₄cycloalkyl,C₃-C₆alkynyl, C₁-C₆alkylcarbonyl, C₁-C₆halogenoalkylcarbonyl,C₂-C₆alkenylcarbonyl, C₂-C₆halogenoalkenylcarbonyl, C₁-C₆alkylsulfonylor C₁-C₆halogenoalkylsulfonyl;

n, is 0, 1 or 2;

R₄ is hydrogen, C₁-C₄alkyl, C₁-C₄halogenoalkyl, C₃-C₆alkenyl,C₃-C₄halogenoalkenyl, C₃-C₆alkynyl or C36ecycloalkyl;

R₅ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄halogenoalkyl, cyano, nitro,amino, NH₂C(S)—, C₁-C₄alkylcarbonyl, C₁-C₄halogenoalkylcarbonyl,C₂-C₄alkenylcarbonyl, C₂-C₄halogenoalkenylcarbonyl orC₂-C₄alkynylcarbonyl;

R₁₁ is hydrogen, fluorine, chlorine, bromine or methyl;

R₁₃ is hydrogen, halogen, cyano, CIS(O)₂—, CIC(O)—, nitro, amino,

R₂₀NH— or R₂₀R₂₁N—;

R₂₀ and R₂₁ independently of one another are C₁-C₈alkyl, C₃-C₈alkenyl,C₃-C₉alkynyl, C₃-C₆cycloalkyl, C₁-C₈halogenoalkyl, C₃-C₈halogenoalkenyl,C₁-C₄alkylcarbonyl, C₁-C₄-halogenoalkylcarbonyl, C₁-C₄alkylsuffonyl,C₁-C₄halogenalkylsulfonyl, benzyl or benzyl which is substituted on thephenyl ring once to three times by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl; or

R₁₃ is R₃₀O—;

R₃₀ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₃-C₆cycloalkyl, C₁-C₈halogenoalkyl, C₃-C₈halogenoalkenyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆alkenyloxy-C₁-C₄alkyl,C₃-C₆lkynyloxy-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkoxy-C₁-C₄alkyl,C₁-C₄alkylthio-C₁-C₄alkyl, C₁-C₈alkoxycarbonyl, C₃-C₈alkenyloxycarbonyl,benzyloxycarbonyl, phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl orpyridazinyl, where these aromatic and heteroaromatic rings mentioned canbe unsubstituted or substituted once to three times by halogen,C₁-C₄alkyl or C₁-C₄halogenoalkyl; or

R₃₀ is R₃₁X₁C(O)—C₁-C₉alkyl- or

X₁ is oxygen, sulfur or

R₃, is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₃-C₆cycloalkyl, C₁-C₈-halogenoalkyl, C₃-C₈halogenoalkenyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆alkenyloxy-C₁-C₄alkyl,C₁-C₄alkyl-thio-C₁-C₄alkyl, phenyl, phenyl which is substituted once tothree times by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl, benzyl orbenzyl which is substituted once to three times on the phenyl ring byhalogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl;

R₃₂ is hydrogen, C₁-C₈alkyl, C₃-G₈alkenyl, C₃-C₈alkynyl, C₃-C₆cycloalkylor C₁-C₈-halogenoalkyl; or

R₁₃ is R₃₃S(O)_(n2)—;

n₂ is 0, 1 or 2;

R₃₃ is C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₃-C₆cycloalkyl,C₁-C₈halogenoalkyl, C₃-C₈halogenoalkenyl, C₁-C₄alkoxy-C₁-C₄alkyl,C₃-C₆alkenyloxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenylwhich is substituted once to three times by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl, benzyl or benzyl which is substituted once to threetimes on the phenyl ring by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl,and, if n₂ is 0,

R33 is hydrogen, C₁-C₈alkylcarbonyl or R₃₄X₂C(O)—;

X₂ is oxygen, sulfur or

R₃₄ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₃-C₆cycloalkyl, C₁-C₈-halogenoalkyl, C₃-C₈halogenoalkenyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆alkenyloxy-C₁-C₄alkyl,C₁-C₄alkyl-thio-C₁-C₄alkyl, phenyl, phenyl which is substituted once tothree times by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl, benzyl orbenzyl which is substituted once to three times on the phenyl ring byhalogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl;

R₃₅ is hydrogen, C₁-C₈alkyl or C₃-C₈alkenyl; or

R₁₃ is R₃₆R₃₇NS(O)₂—;

R₃₆ is hydrogen, C₁-C₈alkyl, C₂-C₈alkenyl, C₃-C₈alkynyl orC₃-C₈cycloalkyl;

R₃₇ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₁-C₈halogenoalkyl, C₁-C₄-alkylcarbonyl, C₁-C₄halogenoalkylcarbonyl,benzoyl or benzoyl which is substituted once to three times on thephenyl ring by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl;

R₁₃ is R₄₀C(O)—;

R₄₀ is hydrogen, fluorine, chlorine, C₁-C₈alkyl, C₂-C₈alkenyl,C₂-C₈alkynyl, C₃-C₆cycloalkyl, C₁-C₈halogenoalkyl, cyano-C₁-C₄alkyl,C₂—C₈alogenoalkenyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆alkenyloxy-C₁-C₄alkyl,C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenyl which is substituted once tothree times by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl, benzyl orbenzyl which is substituted once to three times on the phenyl ring byhalogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl; or

R₁₃ is R₅₀X₃C(O)—;

X₃ is oxygen, sulfur,

R₅₀ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₃-C₆cycloalkyl, C₁-C₈-halogenoalkyl, C₃-C₈halogenoalkenyl,cyano-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆alkenyloxy-C₁-C₄alkyl,(oxiranyl)—CH₂—, oxetanyl-, C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenylwhich is substituted once to three times by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl, benzyl or benzyl which is substituted once to threetimes on the phenyl ring by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl,phenyl-C₂-C₆alkyl, C₁-C₆alkyl-CO—C₁-C₄alkyl,

R₅₃X₄C(O)—C₁-C₆alkyl,

or R₅₃X₄C(O)—C₃-C₆cycloalkyl;

X₄ oxygen, sulfur,

R₅₃ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₃-C₆cycloalkyl, C₁-C₈-halogenoalkyl, C₃-C₈halogenoalkenyl,cyano-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆-alkenyloxy-C₁-C₄alkyl,(oxiranyl)—CH₂—, oxetanyl-, C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenylwhich is substituted once to three times by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl, benzyl, benzyl which is substituted once to threetimes on the phenyl ring by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl,or phenyl-C₂-C₆alkyl;

R₅₁, R₅₂, R₅₄ and R₅₅ independently of one another are hydrogen,C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₁-C₈halogenoalkyl or benzyl; or

R₁₃ is B₁-C₁-C₈alkyl, B₁-C₂-C₈alkenyl, B₁-C₂-C₈alkynyl,B₁-C₁-Calogenoalkyl, B₁-C₂-C₈halogenoalkenyl, B₁-C₁-C₄alkoxy-C₁-C₄alkyl,B₁-C₁-C₄alkylthio-C₁-C₄alkyl or B₁-C₃-C₆cycloalkyl;

B₁ is hydrogen, cyano, hydroxyl, C₁-C₄alkoxy, C₃-C₈alkenyloxy,R₆₀X₅C(O)—, C₁-C₄-alkylcarbonyl or C₁-C₄halogenoalkylcarbonyl;

X₅ has the meaning of X₄;

R₆₀ has the meaning of R₅₃; or

R₁₃ is B₂-C(R₇₀)═CH—;

B₂ is nitro, cyano or R₇₁X₆C(O)—;

R₇₀ is cyano or R₇₂X₇C(O)—;

X₆ and X₇ have the meaning of X₄; and

R₇₁ and R₇₂ have the meaning of R₅₃,

and the pyrazole N-oxides, agrochemicaiy tolerated salts andstereoisomers of these compounds of the formula I, the compounds of theformulae I₀₁, I₀₂, I₀₃ and I₀₄ being excluded:

In the abovementioned definitions, halogen is to be understood asmeaning iodine and, preferably, fluorine, chlorine and bromine.

The alkyl, alkenyl and alkynyl groups occurring in the substituentdefinitions can be straight-chain or branched, this also applying to thealkyl, alkenyl and alkynyl moiety of the alkylcarbonyl, alkylcarbamoyl,hydroxyalkyl, cyanoalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, alkylthio,alkylthioalkyl, alkylthio-C(O), alkenylcarbamoyl, alkenylthio-C(O),alkynylthio-C(O), alkylsuffonyl, alkylaminocarbonyl,dialkylaminocarbonyl, alkylcarbonylalkyl, Bialkyl, Bialkenyl, Bialkynyl,HOC(O)alkyl, phenylalkyl, R₅₃X₄C(O)—C₁-C₆alkyl and RaoX₅C(O)—C₁-C₈-alkylgroups.

Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, iso-butyl, tert-butyl and the various isomericpentyl, hexyl, heptyl and octyl radicals. Methyl, ethyl, n-propyl,iso-propyl and n-butyl are preferred.

Examples of alkenyls are vinyl, allyl, methallyl, 1-methylvinyl,but-2-en-1-yl, pentenyl, 2-hexenyl, 3-heptenyl and 4-octenyl, preferablyalkenyl radicals having a chain length of 3 to 5 carbon atoms.

Examples of alkynyls are ethynyl, propargyl, 1-methylpropargyl,3-butynyl, but-2-yn-1-yl, 2-methylbutyn-2-yl, but-3-yn-2-yl, 1-pentynyl,pent-4-yn-1-yl or 2-hexynyl, preferably alkynyl radicals having a chainlength of 2 to 4 carbon atoms.

Halogenoalkyl can be alkyl groups which are substituted once or severaltimes, in particular once to three times, by halogen, halogen beingiodine and, in particular, fluorine, chlorine and bromine, for examplefluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl,2-chloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl and2,2,2-trichloroethyl.

Halogenoalkenyl can be alkenyl groups which are substituted once orseveral times by halogen, halogen being specifically bromine, iodineand, in particular, fluorine and chlorine, for example 2- and3-fluoropropenyl, 2- and 3-chloropropenyl, 2- and 3-bromopropenyl,2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl,4,4,4-trifluoro-but-2-en-1-yl and 4,4,4-trichloro-but-2-en-1-yl. Of thealkenyl radicals substituted once, twice or three times by halogen,those which have a chain length of 3 or 4 carbon atoms are preferred.The alkenyl groups can be substituted by halogen on saturated orunsaturated carbon atoms.

Alkylsulfonyl is, for example, methylsulfonyl ethylsulfonyl,propylsulfonyl, iso-propylsulfonyl, n-butylsulfonyl, iso-butylsulfonyl,sec-butylsulfonyl and tert-butylsulfonyl; preferably methylsulfonyl andethylsulfonyl.

Halogenoalkylsulfonyl is, for example, fluoromethylsulfonyl,difluoromethylsulfonyl, trifluoromethylsuffonyl, chloromethylsulfonyl,trichloromethylsulfonyl, 2-fluoroethylsulfonyl,2,2,2-trifluoroethylsulfonyl and 2,2,2-trichloroethylsulfonyl.

Alkenylsulfonyl is, for example, allylsulfonyl, methallylsulfonyl,but-2-en-1-yl-sulfonyl, pentenyisulfonyl and 2-hexenyisulfonyl.

Halogenoalkenylsulfonyl is, for example, 2- and3-fluoropropenyl-sulfonyl, 2- and 3-chloropropenyl-sulfonyl, 2- and3-bromopropenyl-sulfonyl, 2,3,34rifluoropropenyl-sulfonyl,2,3,3-trichloropropenyl-sulfonyl, 4,4,4-trifluoro-but-2-en-1-yl-sulfonyland 4,4,4-trichloro-but-2-en-1-yl-sulfonyl.

Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1-yl andcyanopropyl. Hydroxyalkyl is, for example, hydroxymethyl, 2-hydroxyethyland 3-hydroxypropyl.

Alkylamino is, for example, methylamino, ethylamino and the isomericpropyl- and butylamino.

Dialkylamino is, for example, dimethylamino, diethylamino and theisomeric dipropyl- and dibutylamino.

Alkenylamino is, for example, allylamino, methallylamino andbut-2-en-1-ylamino.

Alkynylamino is, for example, propargylamino and 1-methylpropargylamino.

Halogenoalkylamino is, for example, chloroethylamino,trifluoroethylamino and 3-chloropropylamino.

Di(halogenoalkyl)amino is, for example di(2-chloroethyl)amino.

Alkylcarbonyl is, in particular, acetyl and propionyl.

Halogenoalkylcarbonyl is, in particular, trifluoroacetyl,trichloroacetyl, 3,3,3-trifluoropropionyl and 3,3,3-trichloropropionyl.

Alkenylcarbonyl is, in particular, vinylcarbonyl, allylcarbonyl,methallylcarbonyl, but-2-en-1-yl-carbonyl, pentenylcarbonyl and2-hexenylcarbonyl.

Alkynylcarbonyl is, in particular, acetylenecarbonyl, propargylcarbonyl,1-methylpropargyl- carbonyl, 3-butynylcarbonyl, but-2-yn-1-yl-carbonyland pent-4-yn-1-yl-carbonyl.

Alkenyloxy is, for example, allyloxy, methallyloxy and but-2-en-1-yloxy.

Alkynyloxy is, for example, propargyloxy and 1-methylpropargyloxy.

Alkoxy-alkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,ethoxyethyl, n-propoxymethyl, n-propoxyethyl, iso-propoxymethyl andiso-propoxyethyl.

Alkenyloxy-alkyl is, for example, aliyloxy-alkyl, methallyloxy-alkyl andbut-2-en-1-yloxy-alkyl. Alkynyloxy-alkyl is, for example,propargyloxy-alkyl and 1-methylpropargyloxy-alkyl.

Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl,n-propoxycarbonyl, iso-propoxycarbonyl and n-butoxycarbonyl, preferablymethoxycarbonyl and ethoxycarbonyl.

Alkenyloxycarbonyl is, for example, allyloxycarbonyl,methallyloxycarbonyl, but-2-en-1-yl-oxycarbonyl, pentenyloxycarbonyl and2-hexenyloxycarbonyl.

Alkynyloxycarbonyl is, for example, propargyloxycarbonyl,3-butynyloxycarbonyl, but-2-yn-1-yl-oxycarbonyl and2-methylbutyn-2-yl-oxycarbonyl.

Alkoxyalkoxycarbonyl is, for example, methoxymethoxycarbonyl,ethoxymethoxycarbonyl, ethoxyethoxycarbonyl, propoxymethoxycarbonyl,propoxyethoxycarbonyl, propoxypropoxycarbonyl and butoxyethoxycarbonyl.

Halogenoalkoxy is, for example, fluoromethoxy, difluoromethoxy,trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy,2-fiuoroethoxy, 2-chloroethoxy and 2,2,2-trichloroethoxy.

The cycloalkyl radicals which are suitable substituents are, forexample, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The cycloalkoxycarbonyl radicals which are suitable substituents are,for example, cyclopropoxycarbonyl, cyclobutoxycarbonyl,cyclopentoxycarbonyl and cyclohexyloxycarbonyl.

Alkylthio is, for example, methylthio, ethylthio, propylthio andbutylthio and branched isomers thereof.

Alkylthioalkyl is, for example, methylthioethyl, ethylthioethyl,methylthiopropyl and ethyfthiopropyl.

Halogenoalkylthio-carbonyl is, for example, fluoromethylthio-carbonyl,difluoromethylthio-carbonyl, trffluoromethylthio-carbonyl,2,2,2-trifluoroethylthio-carbonyl,1,1,2,2-tetrafluoroethylthio-carbonyl, 2-fluoroethylthio-carbonyl,2-chloroethylthiocarbonyl and 2,2,2-trichloroethylthio-carbonyl.

Phenyl, benzyl or benzoyl as part of a substituent, for example phenoxy,phenylthio, benzyloxy, benzylthio, phenoxycarbonyl, benzyloxycarbonyl,phenoxycarbonylalkyl, benzyloxycarbonylalkyl or benzylamino, are presentin substituted or unsubstituted form. The substituents can then be inthe ortho-, meta- or para-position. Substituents, are, for example,C₁-C₄alkyl, halogen or C₁-C₄halogenoalkyl.

Corresponding definitions can also be assigned to the substituents incomposite definitions, for example halogenoalkenylcarbonyl,alkenyloxy-alkoxy, alkynyloxy-alkoxy, alkoxy-alkoxy-alkoxy,alkylthio-alkylamino, alkylthio-alkylthio, alkoxy-alkylthio,alkenyloxy-alkythio, alkenyloxy-alkylamino, R₃₀O—, R₄₀C(O)—,R₃₃S(O)_(n2)—, R₃₄X₂C(O)—, R₆₀X₃C(O)—, R₃₁X₁C(O)alkyl,R₅₃X₄C(O)cycloalkyl, R₃₆R₃₇NS(O)₂—, B₁alkyl, B₁alkenyl, B₁alkynyl,B₁halogenoalkyl, B₁halogenoalkenyl, B₁alkoxyalkyl, B₁alkylthioalkyl,B₁cycloalkyl and E₂—C(R₇₀)═CH—.

In the definition of R₃₀, the group

means that the R₃₁X₁C(O)—substituted C₁-C₈glkylene chain is additionallysubstituted by phenyl on one of the 8 carbon atoms, where the phenylring can be substituted once to three times by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl and the alkylene chain can be straight-chain orbranched and can be, for example, methylene, ethylene, methylethylene,propylene, 1-methyl-propylene and butylene.

In the definition of R₅₀, the groups

mean that the C₁-C₆alkyl-C(O)— or R₅₃X₄C(O)-substituted C₁-C₄orC₁-C₆alkylene chain is additionally substituted by phenyl (C₆Hs) on oneof the 4 or, respectively, 6 carbon atoms, where the phenyl ring can besubstituted once to three times by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl and the alkylene chain can be straight-chain orbranched and can be, for example, methylene, ethylene, methylethylene,propylene, 1-methyl-propylene and butylene.

In the definitions for cyanoalkyl, alkylcarbonyl, alkenylcarbonyl,halogenoalkenyl-carbonyl, alkynylcarbonyl, alkoxycarbonyl andhalogenoalkylcarbonyl, the cyano or, respectively, carbonyl carbon atomis not included in the respective lower and upper carbon number limitsstated.

In respect of the group W (W1 to W3), the compounds of the formula I arein general present as mixtures comprising the isomers substituted by thepyridyl group (pyrid) in the 3- and 5-position of the pyrazole ring, forexample as isomers IW1a and IW1b

for the group W1. The isomer ratio can vary according to the synthesisprocess.

The invention also relates to the salts which the compounds of theformula I with acid hydrogen, in particular the derivatives withcarboxylic acid and sulfonamide groups (for example carboxyl-substitutedalkyl, alkylene, alkenyl, alkynyl, alkoxyalkyl, alkylfthioalkyl andcycloalkyl groups and NH₂SO₂—, alkylS(O)₂NH— andhalogenoalkylS(O)₂NH-substituted pyridyl groups (R₁₃)), can form withbases. These salts are, for example, alkali metal salts, for examplesodium and potassium salts; alkaline earth metal salts, for examplecalcium and magnesium salts; ammonium salts, i.e. unsubstituted ammoniumsalts and mono- or polysubstituted ammonium salts, for exampletriethylammonium and methylammonium salts; or salts with other organicbases.

Preferred alkali metal and alkaline earth metal hydroxides assalt-forming agents are, for example, the hydroxides of lithium, sodium,potassium, magnesium or calcium, and in particular those of sodium andpotassium.

Examples of amines which are suitable for ammonium salt formationinclude ammonia and primary, secondary and tertiary C₁-C₁₈alkylamines,C₁-C₄hydroxyalkylamines and C₂-C₄-alkoxyalkylamines, for examplemethylamine, ethylamine, n-propylamine, iso-propylamine, the fourisomeric butylamines, n-amylamine, iso-amylamine, hexylamine,heptylamine, octylamine, nonylamine, decylamine, pentadecylamine,hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine,methyl-iso-propylamine, methyl-hexylamine, methyl-nonylamine,methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine,ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine,hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine,di-iso-propylamine, di-n-butylamine, di-n-amylamine, di-iso-amylamine,dihexylamine, diheptylamine, dioctylamine, ethanolamine,n-propanolamine, iso-propanolamine, N,N-diethanolamine,N-ethylpropanolamine, N-butylethanolamine, allylamine,n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine,di-butenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine,triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-n-butylamine,tri-iso-butylamine, tri-sec-butylamine, tri-n-amylamine,methoxyethylamine and ethoxyethylamine; heterocyclic amines, for examplepyridine, quinoline, iso-quinoline, morpholine, thiomorpholine,piperidine, pyrrolidine, indoline, quinuclidine and azepine; and primaryarylamines, for example, anilines, methoxyanilines, ethoxyanilines, o-,m- and p-toluidines, phenylenediamines, benzidines, naphthylamines ando-, m- and p-chloroanilines; and in particular triethylamine,iso-propylamine and di-iso-propylamine.

The salts of the compounds of the formula I with basic groups, inparticular with basic pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl andpyrazolyl rings, or of the derivatives with amino groups, for examplealkylamino and dialkylamino groups, in the definition of R₃, R₅ and R₁₃are, for example, salts with inorganic and organic acids, for examplehydrogen halide acids, such as hydrofluoric acid, hydrochloric acid,hydrobromic acid or hydroiodic acid, and sulfuric acid, phosphoric acidand nitric acid, and organic acids, such as acetic acid, trifluoroaceticacid, trichloroacetic acid, proprionic acid, glycolic acid, thiocyanicacid, citric acid, benzoic acid, oxalic acid, formic acid,benzenesulfonic acid, p-toluenesulfonic acid and methanesuffonic acid.

The possible presence of at least one asymmetric carbon atom in thecompounds of the formula I, for example in the substituent R₁₃═OR₃₀, inwhich R₃₀ is a branched alkyl, alkenyl, halogenoalkyl or alkoxyalkylgroup, or R₁₃═S(O)_(n2)R_(33,) in which, for example, n₂=1 and/or R₃₃ isa branched alkyl, alkenyl, halogenoalkyl or alkoxyalkyl group, meansthat the compounds can occur both in optically active individual isomersand in the form of racemic mixtures. In the present invention, theactive compounds of the formula I are to be understood as meaning boththe pure optical antipodes and the racemates or diastereomers.

If an aliphatic C═C double bond is present, geometric isomerism canoccur. The present invention also relates to these isomers.

Preferred compounds of the formula I are those in which R₃ is hydrogen,C₁-C₄alkyl, C₁-C₄halogenoalkyl, C₂-C₆alkenyl, C₂-C₆alogenoalkenyl,C₂-C₆alkynyl, halogen, cyano, NH₂C(S)—, nitro or R₁₈R₁₉N—.

Preferred compounds of the formula I have the formula Ia

in which

Wa is a group

R₁, R₂, R₃, R₄, R₅, R₁₁, R₁₃ and n₁ are as defined under formula I; and

R₁₂ is hydrogen, halogen, C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl,C₁-C₄halogenoalkyl, C₂-C₄-halogenoalkenyl, nitro, amino, CHO,C₁-C₄halogenoalkoxy, cyano, C₃-C₆cycloalkyl, phenoxy, phenoxy which issubstituted once to three times by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl, benzyloxy or benzyloxy which is substituted once tothree times on the phenyl ring by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl.

Particularly preferred compounds are those of the formula Ia in which R₃is methyl, C₁-C₄halogenoalkyl, chlorine or bromine. Of these, thosecompounds in which Wa is the group W1a are especially preferred.

Compounds which are also especially preferred are those of the formula1a in which Wa is the group W3a; and R₃ is methyl, C₁-C₄halogenoalkyl,chlorine or bromine.

Compounds which are likewise especially preferred are those of theformula Ia in which Wa is the group W3a; and R₃ is methyl,C₁-C₄halogenoalkyl, chlorine or bromine.

Particularly preferred compounds of the formula Ia are those in which Wais the group W3a; and R₃ is R₁₈R₁₉N—.

Particularly important compounds of the formula Ia are those in which Wais the group W1a; R₁ is C₁-C₄alkyl; R₂ is C₁- or C₂halogenoalkyl; R₃ ischlorine or bromine; A is ═N—; R₁, is fluorine, chlorine or bromine; R₁₂is halogen; and R₁₃ is hydrogen. Of these, those in which R₁ is methylor ethyl; R₂ is halogenomethyl; R₃ is chlorine; R₁₁ is fluorine; and R₁₂is chlorine are particularly important; and in particular, of thesecompounds, that in which R₁ is methyl; and R₂ is difluoromethyl isespecially important.

The process according to the invention for the preparation of compoundsof the formula I is carried out analogously to known processes, asdescribed, for example, in WO 96/01254 and WO 97/00246, and comprises,for the purpose of preparation of those compounds of the formula I

in which W is a group

A and n₁₃ are as defined under formula I; and R₃ is hydrogen, halogen,C₁-C₄alkyl or C₁-C₄halogenoalkyl, for example reacting a compound of theformula X

in which R₁₁, R₁₃ and n₁₃ are as defined, in an alcohol of the formulaXV

R₈—OH  (X),

in which R₈ is C₁-C₄alkyl, in the presence of a suitable palladium ornickel catalyst, for example palladium bis(triphenylphosphine)dichloride(PdCl₂(PPh₃)₂), and a base, for example triethylamine, under anincreased pressure of carbon monoxide to give the compound of theformula XI

in which R₈, R₁₁, R₁₃ and n₁₃ are as defined, hydrolysing this underacid or basic conditions to give the corresponding carboxylic acid ofthe formula XII

and converting this with a carboxylic acid halogenating reagent, forexample thionyl chloride, phosphorus pentachloride or oxalyl chloride,into the corresponding carboxylic acid halide of the formula XIII

in which R₁₁, R₁₃ and n₁₃ are as defined; and Hal is halogen, preferablychlorine, and reacting this in a solvent, for example acetonitrile, inthe presence of an alkaline earth metal salt, preferably magnesiumchloride, and a base, for example triethylamine, with the malonic acidmonoester salt of the formula XVI

in which R₃ is hydrogen,, C₁-C₄alkyl or C₁-C₄halogenoalkyl; M₁ ⁺ is analkali metal ion, preferably a potassium ion; and R₇ is C₁-C₄alkoxy, togive the keto ester of the formula III

in which R₃, R₇, R₁₁, R₁₃ and n₁₃ are as defined, and cyclizing this ina solvent, for example glacial acetic acid, with the compound of theformula XIV

NH₂NH—R₁  (XIV),

in which R₁ is as defined under the formula I, to give the compound ofthe formula Ic

in which R₁, R₃, R₁₁, R₁₃ and n₁₃ are as defined, and then, by standardprocesses, functionalizing, in particular freonizing, the hydroxylgroup, according to the definition of R₂, if appropriate halogenatingthe pyrazole ring (R₃ halogen), or oxidizing the compound to thecorresponding pyridine N-oxide.

All further compounds originating from the scope of the formula I caneasily be prepared in an analogous manner, in respect of the build-up ofthe pyrazole ring, to that described in Preparation Examples H1 to H34,or to that described, for example, in “Methoden der Organischen Chemie”[Methods of organic chemistry] (Houben-Weyl), Volume E 8b, Georg ThiemeVerlag Stuttgart, 1994, page 399 et seq.; or in “Pyrazoles, Pyrazolines,Pyrazolidines, Indazoles and Condensed Rings”, Editor R. H. Wiley,Interscience Publishers, John Wiley & Sons, New York, 1967, page 1 etseq.; or to that described in the following patent specifications EP-A-0361 114, U.S. Pat. No. 5,032,165, WO 92/02509, WO 92/06962, WO 95/33728and WO 96/01254, taking into account the chemical properties of thepyridyl moiety.

A large number of known standard processes are available for thepreparation of the pyridylpyrazoles of the formula I substituted on thepyridyl ring, the choice of suitable preparation processes depending onthe properties (reactivties) of the substituents in the particularintermediate. Some examples are described in Preparation Examples H1 toH34.

The starting compounds 2,5-dichloro-3-fluoropyridine,2,3-dichloro-5-trifluoromethylpyridine and 3,5-dichloro-2-acetylpyridineused in Preparation Examples H1, H2 and H11 and the compounds of theformulae X, XIV and XVI are either known or can be prepared by processesanalogous to disclosed processes.

For the preparation of the compounds of the formula I, in particular inwhich W is a group W3; R₅ is halogenoalkyl (Example H11); and R₁, R₃,R₁₁, R₁₃, A and n₁₃ are as defined under formula I, the compounds of theformula II

in which A, R₁, R₃, R₁₁, R₁₃ and n₁₃ are as defined in claim 1; R₀₅ isHOC(O)—, CIC(O)—, (CH₃O)(CH₃)N—C(O)—, C₁-C₄alkyloxycarbonyl, NH₂C(O)—,OHC—, R₆O—N═CH—, HON═CH—, (C₁-C₄alkoxy)₂CH—, C₁-C₄alkyl-CH (OH)—,C₁-C₄halogenoalkyl-CH(OH)—, C₂-C₄alkenyl-CH(OH)—,C₂-C₄halogenoalkenyl-CH(OH)— or C₂-C₄alkynyl-CH(OH)—; and R₆ isC₁-C₄alkyl, C₁-C₄halogenoalkyl, C₁-C₄alkylcarbonyl,C₁-C₄halogenoalkylcarbonyl, C₁-C₄alkylsulfonyl orC₁-C₄halogenoalkylsuffonyl, are important intermediates.

The compounds of the formula IV are prepared in accordance with EP-A-0361 114, U.S. Pat. No. 5,032,165, WO 92/02509, WO 92/06962, WO 95/33728and WO 96/01254.

For the preparation of the compounds of the formula I in which W is agroup

R₁, R₂, R₁₁, R₁₃, A and n₁₃ are as defined under

formula I; and R₃ is hydrogen, halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl, the compounds of the formula III

in which A, R₁₁, R₁₃ and n₁₃ are as defined under formula I; R₃ ishydrogen, C₁-C₄alkyl, halogen or C₁-C₄halogenoalkyl; and R₇ isC₁-C₄alkoxy, C₁- or C₂halogenoalkyl or C₁-C₄alkoxycarbonyl, thecompounds of the formula III₀₁, and III₀₂

being

excluded, are important intermediates.

For the preparation of the compounds of the formula Ia in which W is agroup W3a; R₅ is hydrogen; and R₁, R₃, R₁₁, R₁₃, A and n₁₃ are asdefined under formula I, the compounds of the formula IV

in which A, R₁₁, R₁₃ and n₁₃ are as defined under formula l; and R₃ ishydrogen, halogen, C₁-C₄alkyl or C₁-C₄hatogenoalkyl, are importantintermediates.

The compounds of the formula IV are prepared in accordance with EP-A-0361 114, U.S. Pat. No. 5,032,165, WO 92/02509, WO 92/06962, WO 95/33728and WO 96/01254.

For the preparation of the compounds of the formula I in which W is agroup W3

R₃ is hydrogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl; R₅ is amino;

and R₁, R₁₁, R₁₃, A and n₁₃ are as defined under formula I; thecompounds of the formula V

in which A, R₁₁, R₁₃ and n₁₃ are as defined under formula I; and R₃ ishydrogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl, are important intermediates.

The compounds of the formula V are prepared in accordance with EP-A-0361 114, U.S. Pat. No. 5,032,165, WO 92/02509, WO 92/06962, WO 95/33728and WO 96/01254.

The intermediates of the formulae II, III, IV and V are novel. Theinvention thus also relates to these compounds, excluding the comoundsof the formulae III₀₁ and III₀₂

All further compounds originating from the scope of the formula I caneasily be prepared by processes analogous to those according toPreparation Examples H1 to H34, or in a manner analogous to thatdescribed in “Methoden der Organischen Chemie” [Methods of organicchemistry] (Houben-Weyl), Volume E 8b, Georg Thieme Verlag Stuttgart,1994, page 399 et seq.; ibid, Volume E7B, Georg Thieme Verlag Stuttgart,1992, page 286 et seq.; in “Pyrazoles, Pyrazolines, Pyrazolidines,Indazoles and Condensed Rings”, Editor R. H. Wiley, IntersciencePublishers, John Wiley & Sons, New York, 1967, page 1 et seq.; or in“Comprehensive Heterocyclic Chemistry”, Editors A. R. Katritzky and C.W. Rees, Pergamon Press, Oxford, 1987, or by derivatization by knownstandard methods, as described, for example, in “Advanced OrganicChemistry”, Third Edition, Editor J. March, John Wiley & Sons, New York,1985; in “Comprehensive Organic Transformations”, Editor R. C. Larock,VCH Publishers, Inc., New York, 1989; or in “Comprehensive OrganicFunctional Group Transformations”, Editors A. R. Katritzky, 0.Meth-Cohn, C. W. Rees, Pergamon Press, Oxford, 1995, or as described inthe following patent specifications EP-A-0 361114, US-A-5 032 165, WO92/02509, WO 92106962, WO 95/33728 and WO 96/01254, taking intoconsideration the particular chemical reactivities.

The end products of the formula I can be isolated in the customarymanner by concentration or evaporation of the solvent and can bepurified by recrystallization or trituration of the solid residue insolvents in which they do not dissolve readily, such as ethers, aromatichydrocarbons or chlorinated hydrocarbons, by distillation or by means ofcolumn chromatography and a suitable eluting agent.

The sequence in which certain reactions are advantageously to be carriedout in order possibly to avoid secondary reactions is also familiar tothe expert.

If no controlled synthesis is carried out for isolation of pure isomers,the product can be obtained as a mixture of two or more isomers. Theseisomers can be separated by methods known per se.

The compounds of the formula I or compositions comprising them can beused according to the invention by all the application methods customaryin agriculture, for example preemergence application, postemergenceapplication and seed dressing, and various methods and techniques, forexample controlled release of active substances. For this, the activesubstance is adsorbed in solution onto mineral granule carriers orpolymerized granules (urea/formaldehyde) and dried. If appropriate, acoating which allows the active substance to be released in metered formover a certain period of time can additionally be applied (coatedgranules).

The compounds of the formula I can be employed in unchanged form, i.e.as they are obtained in the synthesis, but they are preferably processedin a customary manner with the auxiliaries conventionally used in theart of formulation, for example to give emulsifiable concentrates,directly sprayable or dilutable solutions, dilute emulsions, wettablepowders, soluble powders, dusts, granules or microcapsules. The methodsof application, such as spraying, atomizing, dusting, wefting,scattering or pouring, in the same way as the nature of thecompositions, are chosen according to the required aims and the givencircumstances.

The formulations, i.e. the compositions, formulations or preparationscomprising the active substance of the formula I or at least one activesubstance of the formula I and as a rule one or more solid or liquidformulation auxiliaries, are prepared in a known manner, for example byintimate mixing and/or grinding of the active substances with theformulation auxiliaries, for example solvents or solid carriers.Surface-active compounds (surfactants) can furthermore additionally beused during preparation of the formulations.

Possible solvents are: aromatic hydrocarbons, preferably fractions C₈ toC₁₂, for example xylene mixtures or substituted naphthalenes, phthalicacid esters, such as dibutyl or dioctyl phthalate, aliphatichydrocarbons, such as cyclohexane or paraffins, alcohols and glycols,and their ethers and esters, such as ethanol, ethylene glycol, ethyleneglycol monomethyl or -ethyl ether, ketones, such as cyclohexanone,strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethylsulfoxide or N,N-dimethylformamide, and epoxidized or non-epoxidizedvegetable oils, such as epoxidized coconut oil or soya oil; or water.

Solid carriers which are as a rule used, for example for dusts anddisposable powders, are natural rock powders, such as calcite, talc,kaolin, montmorillonite or attapulgite. To improve the physicalproperties of the formulation, highly disperse silicic acid or highlydisperse absorbent polymers can also be added. Granular, adsorptivegranule carriers are porous types, for example pumice, crushed brick,sepiolite or bentonite, and non-sorptive carrier materials can be, forexample, calcite or sand. A large number of pregranulated materials ofinorganic or organic nature, such as, in particular, dolomite orcomminuted plant residues, can also be used.

Possible surface-active compounds are nonionic, cationic and/or anionicsurfactants and surfactant mixtures having good emulsifying, dispersingand wetting properties, depending on the nature of the active substanceof the formula I to be formulated.

Suitable anionic surfactants can be both so-called water-soluble soapsand water-soluble synthetic surface-active compounds.

Possible soaps are the alkali metal, alkaline earth metal or substitutedor unsubstituted ammonium salts of higher fatty acids (C₁₀-C₂₂), forexample the Na or K salts of oleic or stearic acid, or of naturallyoccurring fatty acid mixtures, which can be obtained, for example, fromcoconut oil or tallow oil. Fatty acid methyl-taurine salts mayfurthermore also be mentioned.

More often, however, so-called synthetic surfactants are used, inparticular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonatedbenzimidazole derivatives or alkylarylsulfonates.

The fatty alcohol sulfonates or sulfates are as a rule in the form ofalkali metal, alkaline earth metal or substituted or unsubstitutedammonium salts and contain an alkyl radical having 8 to 22 C atoms,alkyl also including the alkyl moiety of acyl radicals, for example theNa or Ca salt of ligninsulfonic acid, of dodecylsulfuric acid ester orof a fatty alcohol sulfate mixture prepared from naturally occurringfatty acids. These also include the salts of sulfuric acid esters andsulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonatedbenzimidazole derivatives preferably contain 2 sulfonic acid groups anda fatty acid radical having 8-22 C atoms. Alkylarylsulfonates are, forexample, the Na, Ca or triethanolamine salts of dodecylbenzenesulfonicacid, of dibutyinaphthalenesulfonic acid or of a naphthalenesulfonicacid/formaldehyde condensation product. Corresponding phosphates, forexample salts of the phosphoric acid ester of ap-nonylphenol-(4-14)-ethylene oxide adduct, or phospholipids canfurthermore also be used.

Nonionic surfactants are, in particular, polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, which can contain 3 to 30 glycol ether groupsand 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to18 carbon atoms in the alkyl radical of the alkylphenols.

Further suitable nonionic surfactants are the water-soluble adducts,containing 20 to 250 ethylene glycol ether groups and 10 to 100propylene glycol ether groups, of polyethylene oxide on polypropyleneglycol, ethylenediaminopolypropylene glycol and alkylpolypropyleneglycol having 1 to 10 carbon atoms in the alkyl chain. The compoundsmentioned usually contain 1 to 5 ethylene glycol units per propyleneglycol unit.

Examples of nonionic surfactants are nonyiphenolpolyethoxyethanols,castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylenesorbitan trioleate, can furthermore also be used.

The cationic surfactants are, in particular, quaternary ammonium saltswhich contain at least one alkyl radical having 8 to 22 C atoms as Nsubstituents, and lower, halogenated or non-halogenated alkyl, benzyl orlower hydroxyalkyl radicals as further substituents. The salts arepreferably present as halides, methyl sulfates or ethyl sulfates, forexample stearyltrimethylammonium chloride orbenzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants conventionally used in the art of formulation and whichcan also be used in the compositions according to the invention aredescribed, inter alia, in “Mc Cutcheon's Detergents and EmulsifiersAnnual” MC Publishing Corp., Ridgewood N.J., 1981, Stache, H.,“Tensid-Taschenbuch” [Surfactant handbook], Carl Hanser Verlag,Munich/Vienna, 1981 and M. and J. Ash, “Encyclopedia of Surfactants”,Vol I-III, Chemical Publishing Co., New York, 1980-81.

The herbicidal formulations as a rule comprise 0.1 to 99% by weight, inparticular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, inparticular 5 to 99.8% by weight, of a solid or liquid formulationauxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, ofa surfactant.

While concentrated compositions are rather preferred as commercialgoods, the end user as a rule uses dilute compositions.

The compositions can also comprise further additives, such asstabilizers, for example epoxidized or non-epoxidized vegetable oils(epoxidized coconut oil, rapeseed oil or soya oil), defoamers, forexample silicone oil, preservatives, viscosity regulators, binders,tackifiers and fertilizers or other active substances.

In particular, preferred formulations have the following compositions:(%=per cent by weight)

Emulsifiable concentrates: Active substance: 1 to 90%, preferably 5 to50% Surface-active agent: 5 to 30%, preferably 10 to 20% Solvent: 15 to94%, preferably 70 to 85% Dusts: Active substance: 0.1 to 50%,preferably 0.1 to 1% Solid carrier: 99.9 to 90%, preferably 999 to 99%Suspension concentrates: Active substance: 5 to 75%, preferably 10 to50% Water: 94 to 24%, preferably 88 to 30% Surface-active agent: 1 to40%, preferably 2 to 30% Wettable powders: Active substance: 0.5 to 90%,preferably 1 to 80% Surface-active agent: 0.5 to 20%, preferably 1 to15% Solid carrier material: 5 to 95%, preferably 15 to 90% Granules:Active substance: 0.1 to 30%, preferably 0.1 to 15% Solid carrier: 99.5to 70%, preferably 97 to 85%

The active substances of the formula I, either as a mixture comprisingthe isomers Ia and Ib or as pure isomers Ia or Ib, can as a rule beemployed successfully on plants or their environment with rates ofapplication of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg/ha. Thedosage required for the desired action can be determined by tests. Itdepends on the nature of the action, the stage of development of thecrop plants and of the weeds and on the application (location, time,method), and can vary within wide limits, depending on these parameters.

The compounds of the formula I and as a rule in particular the isomersof the formula la are distinguished by herbicidal and growth-inhibitingproperties which enable them to be employed in crops of useful plants,in particular in cereals, cotton, soya, sugarbeet, sugarcane,plantations, oilseed rape, maize and rice, and for non-selective weedcontrol (‘Total Vegetation Management’, TVM).

Crops are also to be understood as meaning those which have beenrendered tolerant to herbicides or classes of herbicides by conventionalbreeding or genetic engineering methods. The weeds to be controlled canbe both mono- and dicotyledon weeds, for example Stellaria, Nasturtium,Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum,Phaseolus, Echinochioa, Scirpus, Monochoria, Sagittaria, Bromus,Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida,Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Violaand Veronica.

The following examples illustrate the invention further without limitingit.

PREPARATION EXAMPLES Example H1

Ethyl 3-fluoro-5-chloro-2-pyridinecarboxglate

An autoclave is loaded with 31.4 g of 2,5-dichloro-3-fluoropyridine, 400ml of dry ethanol, 27.8 ml of triethylamine and 3.5 g of palladiumbis(triphenylphosphine) dichloride (PdCl₂(PPh₃)₂), and 180 bar of carbonmonoxide are then forced in. The mixture is then kept at 90° C. for 4days. After cooling and letting down the pressure, a further 3.5 g ofPdCl₂(PPh₃)₂ are added, 130 bar of carbon monoxide are forced in and thetemperature is kept at 90° C. for 3 days. Thereafter, the mixture iscooled to 25° C., the pressure is let down and the autoclave isunloaded. After the mixture has been concentrated in vacuo, the residueis adsorbed onto silica gel from ethyl acetate. After the silica gel hasbeen applied to a flash chromatography column (silica gel), the columnis eluted with n-hexane/ethyl acetate 3/1. 24.3 g of the desired targetcompound of melting point 48-50° C. are obtained.

Example H2

Ethyl 3-chloro-5trifluoromethyl-2-pyridinecarboxylate

An autoclave is loaded with 200 g of2,3-dichloro-5-trifluoromethylpyridine, 1.85 l of ethanol, 260 ml oftriethylamine and 6.5 g of palladium bis(triphenylphosphine)dichloride(PdCl₂(PPh₃)₂). 110 bar of carbon monoxide are then forced in at 25° C.and the mixture is kept at 110° C. for 24 hours. After cooling to 25°C., the crude mixture is concentrated to a thick slurry, which is thenpartitioned between dilute sodium chloride solution and ethyl acetate.After extraction by shaking and separation of the phases, the ethylacetate phase is washed with water, dried over sodium sulfate andconcentrated to dryness. The crude product is distilled under a highvacuum at 0.035 mbar. 200 g of the desired product are obtained as ayellow oil of boiling point 67-70° C./0.035 mbar (yield 85% of theory)

Example H3

3-Chloro-5-trifluoromethyl-2-pyridinecarboxylic acid

423 g of ethyl 3-chloro-5-trifluoromethyl-2-pyridinecarboxylate (ExampleH2) is initially introduced into a mixture of 800 ml of water and 160 mlof ethanol. 800 ml of a 2N sodium hydroxide solution are added dropwiseat a temperature below 35° C. After 3 hours, the mixture is washed twicewith methylene chloride and then rendered acid with an excess ofconcentrated hydrochloric acid, while cooling in an ice-bath. The slurryformed is filtered and the solid is washed with water and dried invacuo. 318 g of the desired product are obtained as a white solid ofmelting point 135° C. (decomposition).

Example H4

3-Fluoro-5-chloro-2-pyridinecarboxylic acid

70 g of ethyl 3-fluoro-5-chloro-2-pyridinecarboxylate (Example H1) areinitially introduced into 105 ml of dimethyl sulfoxide (DMSO). 230 ml ofa 2N sodium hydroxide solution are added dropwise at 40° C. in thecourse of 30 minutes. The resulting yellow suspension is introduced intoa mixture of 2 l of ice-water and 400 ml of 2N hydrochloric acid. Aftersubsequently stirring for 20 minutes, the mixture is filtered and thematerial on the filter is washed twice with water. 56.4 g of the desiredtarget compound are obtained as a white solid.

¹H-NMR (DMSO-D₆): 13.79 ppm (broad signal, 1H); 8.60 ppm (d, 1H); 8.27ppm (dxd, 1H).

Example H5

3-Chloro-5-trifluoromethyl-2-pyridinecarbonyl chloride

89.3 g of 3-chloro-5-trifluoromethyl-2-pyridinecarboxylic acid (ExampleH3) are slowly heated to reflux temperature together with 60 ml ofthionyl chloride and the mixture is then subsequently stirred at thistemperature for 4 hours. Thereafter, it is cooled to 25° C. andconcentrated to dryness in vacuo. Toluene is added twice more and themixture is concentrated again to dryness. 94.0 g of the desired productare obtained as a yellow residue.

¹H-NMR (CDCl₃): 8.91 ppm (d, 1H); 8.13 ppm (d, 1H).

Example H6

3-Fluoro-5-chloro-2-pyridinecarbonyl chloride

71.38 g of 3-fluoro-5-chloro-2-pyridinecarboxylic acid is initiallyintroduced into a round-bottomed flask and heated up to 90° C. 59 ml ofthionyl chloride are added dropwise from a dropping funnel in the courseof 30 minutes, and the gas formed is passed into sodium hydroxidesolution. The mixture is subsequently stirred at 100° C. for a further 5hours. The thionyl chloride is then distilled off under normal pressure.After addition of 50 ml of dry toluene, 20 ml thereof are distilled off.The solution thus obtained is poured onto 200 ml of n-hexane and themixture is stirred overnight. After cooling in an ice-bath, the mixtureis filtered and the material on the filter is washed twice withn-hexane. 68.7 9 of the desired compound are obtained as a brown solid.

¹H-NMR (CDCl₃): 8.60 ppm (d, 1H); 7.69 ppm (dxd, 1H).

Example H7

3-Fluoro-5-chloro-2-pyridinecarboxamide

4.0 g of 3-fluoro-5chloro-2-pyridinecarbonyl chloride (Example H6) areadded in portions to a stirred mixture of 26 ml of 30% aqueous ammoniasolution and 4 ml of tetrahydrofuran. The yellowish suspension issubsequently stirred for 4 hours and filtered and the material on thefilter is washed with water and n-hexane. After drying in vacuo at 40°C., 1.34 g of the desired compound are obtained as a white solid ofmelting point 162-164° C.

The combined aqueous phases are extracted with ethyl acetate. After theorganic phase has been washed and dried, it is filtered and the filtrateis concentrated. A further 6.25 g of the desired target compound areisolated in this manner.

Example H8

3-Fluoro-5-chloro-2-cyanopyridine

1.39 g of 3-fluoro-5-chloro-2-pyridinecarboxamide (Example H7) areinitially introduced into 8 ml of absolute dioxane, and 1.3 ml of drypyridine are added. 1.30 ml of trifluoroacetic anhydride are slowlyadded with a syringe, while stirring and cooling in an ice-bath, and themixture is subsequently stirred for 30 minutes. The resulting reactionmixture is poured onto 1N hydrochloric acid at 25° C. and extracted withdiethyl ether. The ether phase is washed with dilute hydrochloric acid,water, dilute sodium bicarbonate solution and water. After drying oversodium sulfate, the mixture is filtered and the filtrate is concentratedto dryness. 1.14 g of the desired compound are obtained as a slightlyviolet-coloured solid of melting point 72-73° C.

Example H9

3-Chloro-5-trifluoromethyl-2-acetylopridine

55.3 ml of dimethyl malonate are stirred together with 129 ml oftriethylamine and 24.9 g of anhydrous magnesium chloride in 250 ml ofdry toluene for 2 hours. Under an exothermic reaction, the reactiontemperature rises to 45° C. 94.0 g of3-chloro-5-trifluoromethyl-2-pyridinecarbonyl chloride (Example H5) in150 ml of toluene are added dropwise at 25° C. and the reaction mixtureis stirred further overnight. An excess of concentrated hydrochloricacid is then added dropwise, and the mixture is diluted with water andextracted with ethyl acetate. The organic phase is washed with brine,dried over sodium sulfate, filtered and concentrated. 142 g of a red oilare obtained, and the oil is slowly introduced into a mixture of 20 mlof water and 400 ml of dimethyl sulfoxide, which is kept under gentlereflux with the aid of an oil-bath of 150° C. When no further evolutionof gas can be detected, water is added and the mixture is extracted withether. The combined ether phases are washed with water, dried oversodium sulfate, filtered and concentrated. The residue is purified bymeans of column chromatography (silica gel; eluting agent:n-hexanelethyl acetate 15/1 (vN)). 61 g of the desired product areobtained as a yellow oil (70% of theory).

¹H-NMR (CDCA₃): 8.81 ppm (d, 1H); 8.05 ppm (d, 1H); 2.72 ppm (s, 3H).

Example H10

1-3-Chloro-5-trifluoromethyl-2-pyridyl-3-dimethylamino-2-propen-1-one

5.0 g of 3-chloro-5-trifluoromethyl-2-acetylpyridine (Example H9) areinitially introduced into 30 ml of toluene, and 3.60 ml ofN,N-dimethylformamide dimethyl acetal are added. The yellow solutionformed is stirred overnight at 100° C. After cooling to 25° C., it isconcentrated to dryness in vacuo. 6.17 g of the desired target compoundare obtained as a dark yellow oil, which later solidifies.

¹H-NMR (CDCl₃): 8.74 ppm (d, 1H); 7.98 ppm (d, 1H); 7.92 ppm (broadsignal, 1H); 5.54 ppm (broad d, 1H); 3.17 ppm (broad signal, 3H); 2.94ppm (broad signal, 3H).

Example H11

3-(3,5-Dichloro-2-pyridyl)-5-trifluoromethyl-[1 H]-pyrazole

15.8 g of 3,5-dichloro-2-acetylpyridine are initially introduced into125 ml of absolute ether together with 12.0 ml of ethyltrifluoroacetate. The mixture is cooled with an ice-bath, whilestirring, and 46.6 ml of a 21% sodium ethylate solution in ethanol areadded dropwise. Thereafter, the ice-bath is removed and the mixture issubsequently stirred overnight at 25° C. After the reaction mixture hasbeen cooled in an ice-bath and 7.5 ml of glacial acetic acid have beenadded dropwise, the mixture is concentrated in vacuo. 39.0 g of1-(3,5-dichloro-2-pyridyl)-3-trifluoromethyl-propane-1,3-dione, whichcan be used directly for the following cyclization step, are obtained.

39.0 g of 1-(3,5-dichloro-2-pyridyl)-3-trifluoromethyl-propane-1,3-dione

are initially introduced into ethanol, and 4.85 ml of hydrazine hydrateare slowly added. The reaction mixture is then heated to reflux, whilestirring. After 1 hour, it is concentrated to dryness in vacuo and theresidue is partitioned between dilute sodium bicarbonate solution andethyl acetate. After extraction by shaking and separation of the phases,the organic phase is washed with brine, dried over sodium sulfate,filtered and concentrated to dryness. 22.25 g of a yellow oil areobtained, and this is purified by means of flash chromatography (silicagel, eluting agent: n-hexane/ethyl acetate 4/1 (v/v)). 15.0 g of thedesired product are obtained as a yellow solid.

¹H-NMR (DMSO-D₆): 8.81 ppm (m, 1H); 8.64 ppm (m, 1H); 8.26 ppm (m, 1H);7.45 ppm (broad signal, 1H).

Example H123-(3.5-Dichloro-2-pyridyl)-5-trifluoromethyl-1-methyl-[1H]-pyrazole and5-(3,5-dichloro-2-pyridyl)-3-trifluoromethyl-1-methyl-[1H]-pyrazole

8.88 g of 3-(3,5-dichloro-2-pyridyl)-5-trifluoromethyl-[1H]-pyrazole(Example H11) are initially introduced into 35 ml ofN-methylpyrrolidone. After addition of 13.0 g of potassium carbonate,the mixture is stirred and heated up to 55° C. 2.36 ml of methyl iodidein 5.0 ml of N-methylpyrrolidone are then slowly added dropwise. Afterthe mixture has been subsequently stirred for 2 hours, diethyl ether andwater are added, the mixture is extracted by shaking and the organicphase is separated off. The ether phase which has been separated off iswashed with brine, dried over sodium sulfate, filtered and concentrated.The crude product is purified by means of flash chromatography (silicagel; eluting agent: toluene/ethyl acetate 100/1). First, 3.96 g of theisomeric 5-pyridylpyrazole (yield 42%) are isolated as a yellow oil, andthen 1.96 g of the 3-pyridylpyrazoie (yield 21%) are isolated as ayellow solid. The Rf values of the two isomeric 3- and5-pyridyipyrazoles are as follows on silica gel 60 F₂₅₄ withtoluenelethyl acetate 30/1 as the eluting agent (UV):

Rf value 5-pyridylpyrazole: 0.50

Rf value 3-pyridylpyrazole: 0.35

Example H13

3-(3,5-dichloro-2-pyridyl)-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole

2.0 g of3-(3,5-dichloro-2-pyridyl)-5-trifluoromethyl-1-methyl-[1H]-pyrazole(Example H12) are initially introduced into glacial acetic acid at 40°C., and chlorine gas is passed slowly over the solution, while stirring.The reaction can be monitored analytically by means of thin layerchromatography (silica gel 60 F₂₅₄, eluting agent: n-hexane/ethylacetate 4/1, UV). When no further starting material can be detected, theglacial acetic acid is removed in vacuo and the residue is partitionedbetween dilute aqueous sodium hydroxide solution and ethyl acetate.After extraction by shaking, the organic phase which has been separatedoff is washed with brine, dried over sodium sulfate, filtered andconcentrated. The yellow oil is purified by means of flashchromatography (silica gel, eluting agent: n-hexane/ethyl acetate 5/1).1.6 g of the desired compound are obtained as a yellow oil (70% oftheory).

¹H-NMR (DMSO-D₆): 8.80 ppm (d, 1H), 8.48 ppm (d, 1H), 4.11 ppm (s, 3H)

The isomeric 5-pyridylpyrazole is also obtained analogously in a 90%yield (crude).

¹H-NMR (CDCl₃): 8.66 ppm (d, 1H); 7.95 ppm (d, 1H); 3.83 ppm (s, 3H).

Example H14

3-(3-Fluoro-5-chloro-2-pyridyl)-5-hydroxy-1-methyl-[1H]-pyrazole

110.6 g of malonic acid monomethyl ester•potassium salt are initiallyintroduced into 500 ml of absolute acetonitrile. The mixture is cooledin an ice-bath, while stirring, and 109 ml of triethylamine are addeddropwise. 84.3 g of anhydrous magnesium chloride are then added. A mildexothermic reaction is observed. After removal of the ice-bath, themixture is subsequently stirred at 25° C. for 2 hours. After renewedcooling in the ice-bath, 68.7 g of 3-fluoro-5-chloro-2-pyridinecarbonylchloride (Example H6), in several portions, and 300 ml of absoluteacetonitrile are added. A thick slurry gradually forms. The cooling bathis removed and the mixture is subsequently stirred for 5 hours.Thereafter, the reaction mixture is poured onto 3 l of ice-water and 200ml of concentrated hydrochloric acid, subsequently stirred for 15minutes and extracted with ethyl acetate. The organic phase is washedwith water and brine, dried over sodium sulfate, filtered andconcentrated to dryness in vacuo. 110 g of a brown oil, which is useddirectly for the next reaction stage, are obtained.

For this next stage, the brown oil obtained above is introduced at 25°C. into a solution of 20.5 ml of methylhydrazine in 300 ml of glacialacetic acid and the mixture is then stirred at 85° C. for 2 hours. Thebrown suspension formed is introduced, after cooling to 25° C., into 2.5l of ice-water in portions, the mixture is stirred for 1 hour andfiltered and the solid is washed with water and n-hexane. After dryingat 60° C. in vacuo, 65.8 g of the desired title compound of meltingpoint 195-199° C. are obtained.

Example H15

3-(3-Fluoro-5chloro-2-pyridyl)-5-difluoromethoxy-1-methyl-[1H]-pyrazole

46.0 g of3-(3-fluoro-5-chloro-2-pyridyl)-5-hydroxy-1-methyl-[1H]-pyrazole(Example H14) and 84 g of potassium carbonate are initially introducedinto 250 ml of dry dimethylformamide and the mixture is heated up to 85°C. Freon 22 (chlorodifluoromethane) is then passed in over a period of 2hours, with thorough stirring. TLC analysis of a worked-up sample(silica gel 60 F₂₅₄; n-hexane/ethyl acetate/glacial acetic acid 20/20/1,UV) shows that no further starting material is present. The reactionmixture is partitioned between water and diethyl ether (foaming onaddition of water). After extraction by shaking and separation of thephases, the ether phase is washed twice with water and once with brine.After the organic phase has been dried over sodium sulfate and filtered,the filtrate is concentrated in vacuo and the residue is purified bymeans of flash chromatography (silica gel; eluting agent: n-hexane/ethylacetate 2/1 (v/v)). 22.0 g of the desired title compound are obtained asa pale yellow solid.

¹H-NMR (CDCl₃): 8.51 ppm (broad signal, ₁H); 7.56 ppm (dxd, 1H); 6.61ppm (t, 1H); 6.53 ppm (d, 1H); 3.89 ppm (s, 3H).

Example H16

3-(3-Fluoro-5-chloro-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

17.92 g of3-(3-fluoro-5-chloro-2-pyridyl)-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H15) are initially introduced into 60 ml of glacial acetic acidtogether with 10.6 g of sodium acetate. The mixture is heated up to 60°C., while stirring, and a saturated solution of chlorine in glacialacetic acid is added until TLC analysis of a worked-up sample shows acomplete conversion (silica gel 60 F₂₅₄; eluting agent: n-hexane/ethylacetate 2/1; UV; Rf value of the starting material 0.34; Rf value of theproduct 0.48). The mixture is then concentrated to dryness in vacuo andthe resulting residue is partitioned between sodium bicarbonate solutionand ethyl acetate. The organic phase is washed with brine, dried oversodium sulfate, filtered and evaporated to dryness in vacuo. 19.8 g ofthe desired target compound (pure according to TLC) are obtained.Melting point 95-96° C.

Example H18

3-(5-Chloro-2-pyridyl-N-oxide)-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole

6.82 g of3-(5-chloro-2-pyridyl)-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazoleare initially introduced into 30 ml of methylene chloride at 25° C. 7.23g of m-chloroperbenzoic acid are added, while stirring. After 48 hours,a further 2.50 g of m-chloroperbenzoic acid are added. After a further24 hours, the reaction mixture is taken up in ethyl acetate andextracted twice with dilute sodium hydroxide solution, rinsed withbrine, dried over sodium sulfate and concentrated. The residue is thenchromatographed (silica gel; eluting agent. n-hexane/ethyl acetate 1/1(v/v)). 6.31 g of the desired compound are isolated as a white solid.

¹H-NMR (DMSO-D₆): 8.75 ppm (d, 1H); 7.66 ppm (d, 1H); 7.59 ppm (dxd,1H); 4.08 ppm (s, 3H).

Starting from the isomeric5-(5-chloro-2-pyridyl)-4-chloro-3-trifluormmethyl-1-methyl-[1H]-pyrazole,the isomeric5-(5-chloro-2-pyridyl-N-oxide)-4-chloro-3-trifluomomethyl-1-methyl-[1H]-pyrazolecan be obtained in a 70% yield

Example H19

3-(3-Fluoro-5-chloro-2-pyridyl-N-oxide)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

0.57 g of3-(3-fluoro-5-chloro-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H16) is initially introduced into 5 ml of methylene chloride,and 0.63 g of a 55% m-chloroperbenzoic acid is added. After the crudemixture has been stirred at 25° C. for 4 days, it is taken up in ethylacetate and washed successively with sodium bicarbonate solution, waterand brine. After drying over sodium sulfate and filtering, the filtrateis concentrated and the residue is purified by means of flashchromatography. 0.45 g of the desired target compound is obtained as awhite solid of melting point 115-120° C.

Example H20

3-(5,6-Dichloro-2-pyridyl)- and3-(4.5-dichloro-2-pyridyl)-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole(isomer A and B)

20 ml of phosphorus oxychloride (POCl₃) are heated up to 90° C. 10.37 gof3-(5-chloro-2-pyridyl-N-oxide)-4-chloro-5trifluoromethyl-1-methyl-[1H]-pyrazole(Example H18) are introduced in several portions at this temperature,while stirring, and the mixture is subsequently stirred at 90° C. for 1hour. The phosphorus oxychloride is then removed in vacuo and theresidue is taken up in diethyl ether. The organic phase is then washedsuccessively with water, 0.5 N sodium hydroxide solution and brine.After drying over sodium sulfate and filtering, the filtrate isconcentrated. 8.93 g of a brown precipitate are obtained. This crudeproduct is purified by column chromatography (silica gel; eluting agent:n-hexane/ethyl acetate 10/1). First, 0.57 g of isomer B is isolated, andthen 5.11 g of isomer A are isolated as a white solid.

TLC analysis: silica gel 60 F₂₅₄; eluting agent: n-hexane/ethyl acetate4/1 (v/v), UV:

Rf value isomer A: 0.31

Rf value isomer B: 0.41

If 6.3 g of3-(5-chloro-2-pyridyl-N-oxide)-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole(Example H18) are treated with 6.3 g of phosphorus pentachloride in 20ml of phosphorus oxychloride at 90° C. for 1 hour, 4.36 g of isomer Aand 1.01 g of isomer B are obtained after the above working up.

Example H21

3-(3Fluoro-5,6-dichloro-2-pyridyl)- and3-(3-fluoro-4,5dichloro-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole(isomer A and B)

A mixture of 2.1 g of phosphorus pentachloride and 7 ml of phosphorusoxychloride is heated up to 90° C., 2.8 g3-(3-fluoro-5-chloro-2-pyridyl-N-oxide)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H19) is then introduced in portions at this temperature and themixture is stirred at the same temperature for 0.5 hour. Most of thephosphorus oxychloride is then removed in vacuo and the remainingmixture is stirred with warm water and ethyl acetate. The organic phasewhich has been separated off is washed with aqueous sodium bicarbonatesolution and brine. After drying over sodium sulfate and filtering, thefiltrate is concentrated in vacuo and the residue is purified by meansof flash chromatography (silica gel; eluting agent: toluene/ethylacetate 50/1). 0.69 g of isomer A is first isolated as a yellow oil,which later solidifies; melting point 63-67° C. 0.64 g of isomer B isthen obtained as a white solid of melting point 121-123° C.

Example H22

3-(6-Ethoxycarbonyl-5-chloro-2-pyridyl)-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole

An autoclave is loaded with 7.0 g of 3-(5,6-dichloro-2-pyridyl)-4chloro5trifluoromethyl-1-methyl-[1H]-pyrazole (Example H20), 100 ml of dryethanol, 9.0 ml of triethylamine and 0.83 g of palladiumbistriphenylphosphine dichloride (PdCl₂(PPh₃)₂). 140 bar of carbonmonoxide are forced in at 25° C. and the mixture is then kept at 120° C.for 15 hours. After cooling to 25° C., the mixture is concentrated andthe residue is then absorbed onto silica gel from ethyl acetate. Thissilica gel is introduced onto a flash chromatography column and thecolumn is then eluted with a mixture of n-hexane/ethyl acetate 7/1(v/v). 4.51 g of the desired title compound are obtained as a yellowsolid (58% of theory). TLC analysis: Rf value of the product (silica gel60 F₂₅₄, n-hexane/ethyl acetate 4/1 (v/v)): 0.19.

Example H23

3-(6-Chlorocarbonyl-5-chloro-2-pyridyl)-4-chloro-5trifluoromethyl-1-methyl-1-[1H]-pyrazole

5.44 g of3-(6-ethoxycarbonyl-5-chloro-2-pyridyl)-4-chloro-5trifluoromethyl-1-methyl-[1H]-pyrazoleare initially introduced into a flask, and 4.1 ml of a 4 N solution ofsodium hydroxide in 4.1 ml of a mixture of methano/water 2/1 are added.The reaction mixture is heated up to 40° C. and kept at this temperatureovernight. It is then concentrated to dryness under a high vacuum and2.2 ml of thionyl chloride are added to the resulting residue. Themixture is heated up to 80° C. in the course of 2 hours. After coolingto 25° C., it is concentrated to dryness in vacuo. The residue is thendiluted 3 times with carbon tetrachloride and in each case concentratedto dryness in vacuo. 5.56 g of a solid, which is used directly for thenext reaction stage, are obtained.

Example H24

3-[5-Chloro-6-(carboxylic acid 1-allyloxycarbonyl-1-methyl-ethylester)-2-pyridyl]-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole

2.56 g of allyl hydroxyisobutyrate are initially introduced into 15 mlof dry pyridine. 5.30 g of3-(6-chlorocarbonyl-5-chloro-2-pyridyl)-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole (Example H23) are added in several portions at 25° C., underan exothermic reaction, and the mixture is subsequently stirredovernight at 25° C. The reaction mixture is then concentrated in vacuoand the residue is taken up in ethyl acetate. The ethyl acetate phase iswashed successively with water, dilute ammonium chloride solution,water, dilute sodium bicarbonate solution and water. 5.5 g of thedesired title compound are obtained as a brown solid.

¹H-NMR (CDCl₃): 7.94 ppm (d, 1H); 7.84 ppm (d, 1H); 5.94 ppm (m, 1H);5.29 ppm (m, 2H); 4.70 ppm (d, 2H); 4.07 ppm (s, 3H); 1.75 ppm (s, 6H)

Example H25

3-[5-Chloro-6-(carboxylic acid 1-carboxy-1-methyl-ethylester)-2-pyridyl]-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole

3.53 g of 3-[5-chloro-6-(carboxylic acid1-allyloxycarbonyl-1-methyl-ethylester)-2-pyridyl]-4-chloro-5trifluoromethyl-1-methyl-[1 H]-pyrazole(Example H24) are initially introduced into 30 ml of acetonitriletogether with 0.1 g of triphenylphosphine. After five evacuations undera water pump vacuum and subsequent gassing with argon, 0.22 g ofPd(PPh₃)₄ and, after cooling to 0° C., 0.70 ml of pyrrolidine are addedunder argon. The mixture is stirred at 25° C. for 4 hours. It is thenconcentrated in vacuo and the resulting residue is partitioned betweenethyl acetate and a phosphate buffer pH =3. The organic phase is washedwith the buffer solution and then with brine. After drying over sodiumsulfate and filtering, it is concentrated to dryness in vacuo, 3.92 g ofa brown solid remaining. After purification over a flash chromatographycolumn (silica gel; eluting agent: n-hexanelethyl acetate/acetic acid100/100/3), 3.23 g of the desired title compound are obtained.

¹H-NMR (DMSO-D₆): 13.60 ppm (broad signal, 1H); 8.22 ppm (d, 1H); 8.03ppm (d, 1H); 4.11 ppm (s, 3H); 1.62 ppm (s, 6H).

Example H26

3-[5-Chloro-6-(carboxylic acid 1-chlorocarbonyl-1-methyl-ethylester)-2-pyridyl-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole

3.12 g of 3-[5-chloro-6-(carboxylic acid 1-carboxy-1-methyl-ethylester)-2-pyridyl]-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole(Example H 25) are initially introduced into 20 ml of dry toluene andthe mixture is heated up to 80° C. After addition of one drop ofN,N-dimethylformamide, 1.1 ml of thionyl chloride are added dropwise,while stirring. After the mixture has been subsequently stirred at 80°C. for 1 hour, it is cooled to 25° C. and concentrated in vacuo. Afterdissolving the resulting residue in 25 ml of absolute toluene andconcentrating the solution again, 3.21 g of a yellow solid, which isused directly for the next reaction stage, are obtained.

Example H27

3-[5-Chloro-6-(carboxylic acid 1-allylcarbamoyl-1-methyl-ethylester)-2-pyridyl]-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole

0.15 ml of allylamine is initially introduced into 4.0 ml of drypyridine. 0.81 g of 3-[5-Chloro-6-(carboxylic acid1-chlorocarbonyl-1-methyl-ethylester)-2-pyridyl]-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole(Example H26) is added in several portions, while stirring, at atemperature below 5° C. and the mixture is then stirred at 25° C. for 3hours. The resulting dark red solution is partitioned between dilutehydrochloric acid and ethyl acetate. After extraction by shaking andseparation of the phases, the organic phase is washed successively withwater, dilute sodium hydroxide solution and finally with brine. Afterdrying over sodium sulfate, the mixture is filtered and the filtrate isconcentrated to dryness. 0.79 g of the desired title compound isobtained as an orange solid.

¹N-NMR (CDCl₃): 7.99 ppm (d, 1H); 7.89 ppm (d, 1H); 7.07 ppm (broadsignal, 1H); 5.81 ppm (m, 1H); 5.09 ppm (m, 2H); 4.08 ppm (s, 3H); 1.88ppm (s, 6H).

Example H28

3-(5-Chloro-6-methoxy-2-pyridyl)-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole

1.0 g of3-(5,6-dichloro-2-pyridyl)-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole (Example H20) is initially introduced into 5 ml of drydimethoxyethane. After the solution has been cooled to 0° C., 0.61 ml ofa 5.4 molar solution of sodium methylate in methanol is added dropwiseand the mixture is subsequently stirred at 25° C. for 2 days. Thereaction mixture is taken up in diethyl ether and washed successivelywith 0.5 N hydrochloric acid, water and brine. After drying over sodiumsulfate, the mixture is filtered and the filtrate is concentrated todryness in vacuo. 0.94 g of the desired title compound is obtained as awhite solid.

¹H-NMR (DMSO-D₆): 7.99 ppm (d, 1H); 7.50 ppm (d, 1H); 4.08 ppm (s, 3H);4.02 ppm (s, 3H).

Example H29

3-[5-Chloro-6-(imidazol-1-yl)-2-pyridyl]-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole

0.60 g of3-(5,6-dichloro-2-pyridyl)-4-chloro-5-trifluoromethyl-1-methyl-[1]-pyrazole(Example H20), 0.28 g of imidazole and 0.50 g of potassium carbonate areinitially introduced into 10 ml of dry N-methylpyrrolidone. The mixtureis stirred overnight at 100° C. and then cooled to 25° C. andpartitioned between water and diethyl ether. After extraction by shakingand separation of the phases, the ether phase is washed with water,ammonium chloride solution and water. After drying over sodium sulfateand filtering, the filtrate is concentrated in vacuo and the residue ispurified over a flash chromatography column (silica gel; eluting agent:n-hexane/ethyl acetate 1/2). 0.42 g of the desired compound is obtainedas a white solid.

TLC analysis: silica gel 60 F₂₅₄; eluting agent: n-hexane/ethyl acetate1/2;

R₁ value starting material: 0.71

R_(f) value target compound: 0.27.

Example H30

3-(3-Fluoro-5-chloro-6-hydroxy-2-pyridyl)-4-chloro-5-difluoromethoxy-methyl-[1H]-pyrazole

1.0 g of3-(3-fluoro-5-chloro-2-pyridine-N-oxide)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazoleis initially introduced into 12 ml of dry N,N-dimethylformamide. 4.2 mlof trifluoroacetic anhydride is added dropwise from a syringe, whilestirring and cooling with an ice-bath, and the mixture is thensubsequently stirred overnight at 25° C. It is then evaporated in vacuoand the residue is partitioned between diethyl ether and water. Afterextraction by shaking and separation of the phases, the ether phase iswashed with dilute aqueous sodium bicarbonate solution and brine, driedover sodium sulfate, filtered and concentrated. 1.23 g of a yellow oilare obtained, and this is purified by means of flash chromatography(silica gel; eluting agent: n-hexane/ethyl acetate 2/3 (v/v) and 1%glacial acetic acid). 0.59 g of the desired compound is obtained as ayellow solid of melting point 126-128° C.

Example H31

3-(3-Fluoro-5-chloro-6-methoxy-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

0.1 g of3-(3-fluoro-5-chloro-6-hydroxy-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H30) is initially introduced into 2.0 ml of dryN,N-dimethylformamide.

After addition of 0.12 g of dry powdered potassium carbonate, 0.06 g ofmethyl iodide in 1 ml of dry N,N-dimethylformamide is added at 25° C.,while stirring. After 3 hours, the reaction mixture is partitionedbetween water and diethyl ether. The ether phase which has beenseparated off is washed with water and brine, dried over sodium sulfate,filtered and concentrated. After purification over a flashchromatography column (silica gel; eluting agent: n-hexane/ethyl acetate2/1 (v/v)), 0.07 g of the desired product is isolated as a white solid.

TLC analysis: silica gel 60 F₂₅₄; eluting agent: n-hexane/ethyl acetate1/1 (v/v):

R_(f) value product: 0.57

R_(f) value precursor: 0.14.

Example H32

3-(3-Fluoro-5-chloro-2-pyridyl)-4-difluoromethyl-5-difluoromethoxy-1-methyl-[1H]-pyrazole

0.13 g of3-(3-fluoro-5-chloro-2-pyridyl)-4-formyl-5-difluoromethoxy-1-methyl-[1H]-pyrazoleis initially introduced into 3.0 ml of dry 1,2-dichloroethane. 0.11 mlof diethylaminosulfur trifluoride (DAST) is added dropwise with asyringe, while stirring, the reaction mixture assuming a dark colour.The mixture is then stirred at 50° C. for 1 hour. After cooling to 25°C., the reaction solution is applied directly to a flash chromatographycolumn (silica gel) and eluted with n-hexane/ethyl acetate 5/1 (v/v).0.07 g of the desired compound is obtained as a pale yellow solid ofmelting point 79-81° C.

Example H33

3-(3-Fluoro-5-chloro-2-pyridyl)-4-formyl-5-difluoromethoxy-1-methyl-[1H]-pyrazole

2.41 ml of phosphorus oxychloride are introduced into 5 ml ofN,N-dimethylformamide, while cooling in an ice-bath, and the mixture issubsequently stirred at 25° C. for 2 hours. This mixture is then addeddropwise to 5.0 g of3-(3-fluoro-5-chloro-2-pyridyl)-5-hydroxy-1-methyl-[1H]-pyrazole(Example H14) in 15 ml of N,N-dimethylformamide at 80° C. in the courseof 30 minutes. After the mixture has been subsequently stirred at 80° C.for 1.5 hours, it is cooled to 25° C., ice and then water are added andthe mixture is extracted with diethyl ether. After washing the organicphase with water and drying over sodium sulfate, 1.1 g of a yellow solidis obtained as an intermediate. This is initially introduced into 10 mlof dry N,N-dimethylformamide together with 1.72 g of powdered anhydrouspotassium carbonate. The mixture is heated up to 75° C., while stirringthoroughly, and Freon 22 (CHClF₂) is passed in slowly for 7 hours. Themixture is then cooled to 25° C. and taken up in diethyl ether. Theether phase is washed with water and then with brine, dried over sodiumsulfate, filtered and concentrated. 1.50 g of crude product are obtainedas a brown solid, which is purified by means of a flash chromatographycolumn(silica gel; eluting agent: n-hexanelethyl acetate 4/1 (v/v)).0.14 g of the desired target compound is obtained as a yellow solid ofmelting point 111-116° C. in this manner.

Example H34

3-(3-Fluoro-5-chloro-6cyano-2-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

1.50 g of3-(3-fluoro-5-chloro-2-pyridyl-N-oxide)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole (Example H19) are initially introduced into 5 mlof dry acetonitrile, and 1.0 ml of triethylamine is then added. 1.43 mlof trimethylsilyl cyanide in 2 ml of acetonitrile are then addeddropwise at 25° C. in the course of 20 minutes, and the mixture isstirred for 2 days, while heating vigorously under reflux (bathtemperature 110° C.). After cooling to 25° C., the mixture is dilutedwith acetonitrile, adsorbed onto silica gel and introduced onto a flashchromatography column (silica gel). After eluting with a mixture ofn-hexane/ethyl acetate 3/1 (v/v), 0.74 g of the desired product isobtained as a yellow solid of melting point 133-134° C.

Example H35

3-(3-Fluoro-5-chloro-6-vinyl-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

30 g of3-(3-fluoro-5,6-dichloro-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H21) are dissolved in 200 ml of N,N-dimethylformamide (DMF).After addition of 32.9 g of vinyltributyltin, the mixture is twiceevacuated and gassed with argon. A little (i.e. a spatula-tip)2,6-di-tert-butyl-p-cresol and 3.0 g of bistriphenylphosphinepalladiumdichloride (PdCl₂(PPh₃)₂) are then added and the mixture is stirred at atemperature of 67° C. for 24 hours. After cooling to 22° C., thereaction mixture is filtered over Hyflo and partitioned between dilutehydrochloric acid and diethyl ether. The ether phase which has beenseparated off is washed with water, dried over sodium sulfate, filteredand concentrated in vacuo. 84 g of a black oil are obtained, and this ispurified over a silica gel flash column (eluting agent: n-hexanelethylacetate 6/1). The resulting solid is stirred with 100 ml of n-hexane fora further 2 hours, filtered off, washed and dried. 16.4 g of the desiredtitle compound are obtained as a white solid of melting point 75-77° C.

Example H36

3-(3-Fluoro-5-chloro-6-formyl-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

13.2 g of3-(3-fluoro-5-chloro-6-vinyl-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole (Example H35) are initially introduced into a mixture of 120ml of dioxane and 40 ml of water. 16.7 g of sodium (meta)periodate(NalO₄) and a spatula-tip of osmium tetroxide are added, while stirring,and the mixture is subsequently stirred overnight at 22° C. Thefollowing day, the resulting mixture is taken up in ethyl acetate andwashed first with dilute hydrochloric acid and then with brine. Afterdrying over sodium sulfate, the mixture is filtered and the filtrate isconcentrated in vacuo. After purification over a silica gel flash column(eluting agent: n-hexane/ethyl acetate 2/1), 9.4 g of the desired titlecompound are obtained as a white solid of melting point 120-121° C.

Example H37

3-[3-Fluoro-5-chloro-6-(carboxylic acid 1-carboxy-1-methyl-ethylester)-2pyridyl]-4-chloro-5-difluoromethoxy-1-methyl-[1H]-2pyrazole

4.9 g of 3-13-Fluoro-5-chloro-6-(carboxylic acid1-benzyloxycarbonyl-1-methyl-ethylester)-2-pyridyl]-4-chloro-5-difiuoromethoxy-1-methyl-[1H]-pyrazole arehydrogenated with 1.0 g of 5% palladium on active charcoal in 70 ml ofethyl acetate at 22° C. under normal pressure. After 20 minutes, themixture is filtered over Hyflo, dried over sodium sulfate, filtered andconcentrated in vacuo. The resulting crude product is purified over asilica gel flash column (eluting agent: toluene/acetic acid 10/1). 3.8 gof the desired title compound are obtained as a white solid of meltingpoint 133-134° C.

Example H38

3-[3-Fluoro-5-chloro-6-(carboxylic acid1-isopropylmercaptocarbonyl-1-methyl-ethylester)-2-pyridyl]-4-chloro-5-difluoromethogy-1-methyl-[1H]-pyrazole

2.23 g of 3-[3-fluoro-5-chloro-6(carboxylic acid1-carboxy-1-methyl-ethylester)-2-pyridyl]-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H37) are initially introduced into 10 ml of methylene chloride.A catalytic amount of DMF and 0.67 g of oxalyl chloride, in portions,are added to the white suspension (evolution of gas). The mixture issubsequently stirred at 22° C. for 1 hour. The colourless acid chloridesolution thus obtained can be further used directly.

0.64 g of triethylamine and 1 spatula-tip of p-dimethylaminopyridine(DMAP) are initially introduced into 10 ml of ethyl acetate. 0.23 g of2-propanethiol is added, while cooling with ice, and half of the acidchloride solution obtained above is added dropwise in the course of 15minutes. The mixture is then stirred at 22° C. for 3 hours. Thereafter,the remaining amount of 2-propanethiol is removed with argon gas passedover Javelle water. The resulting mixture is diluted with ethyl acetateand washed with dilute hydrochloric acid and then with brine. Theresulting crude product is purified over a silica gel flash column(eluting agent: n-hexane/ethyl acetate 4/1). 1.16 g of a colourless oilwhich slowly crystallizes out are obtained. The solid is comminuted andstirred with 3 ml of n-hexane. After filtration with suction, washingand drying, 1.05 g of the desired title compound are obtained as whitecrystals of melting point 81-82° C.

Example H39

3-(3-Fluoro-5-chloro-6-methacrylic acid ethylester-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

1.00 g of3-(3-fluoro-5-chloro-6-formyl-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H36) is initially introduced into 6 ml of dioxane and 0.1 ml ofwater, and 0.88 g of triethyl 2-phosphonopropionate and 1.44 g ofcaesium carbonate are added. The mixture is then stirred at 80° C. for 2hours and the resulting reaction mixture is diluted with ethyl acetateand washed first with dilute hydrochloric acid and then with brine.After drying over sodium sulfate, filtering and concentrating in vacuo,the residue is purified over a silica gel flash column (eluting agent:toluene/ethyl acetate 10/1). 0.86 g of an isomer A and 0.37 g of anisomer B are obtained.

¹H-NMR (CDCl₃): Isomer A: 7.56 ppm (d, 1H); 6.86 ppm (m, 1H); 6.70 ppm(t, 1H); 4.05 ppm (q, 2H); 3.85 ppm (s, 3H); 2.15 ppm (m, 3H); 1.03 ppm(t, 3H). Isomer B: 7.85 ppm (m, 1H); 7.62 ppm (d,₁H); 6.72 ppm (t, 1H);4.29 ppm (q, 2H); 3.87 ppm (s, 3H); 2.29 ppm (m, 3H); 1.35 ppm (t, 3H).

Example H40

3-(3-Fluoro-5-chloro-2-pyridyl)-5-bromo-1-methyl-[1H]-pyrazole

20.0 g of3-(3-fluoro-5-chloro-2-pyridyl)-5-hydroxy-1-methyl-[1H]-pyrazole(Example H14) are initially introduced into 80 ml of tetrachloroethane.A total of 25.2 g of phosphorus oxybromide (POBr₃) are added in portionsto the brown suspension and the mixture is then stirred at a temperatureof 130° C. for 2 hours. Thereafter, it is cooled and 150 ml of a 2 molarsodium hydroxide solution are added dropwise, while cooling with anice-bath. After addition of diethyl ether and separation of the phases,the organic phase is washed successively with water, dilute hydrochloricacid and brine, dried over sodium sulfate, filtered and concentrated invacuo. 19.94 g of a brown solid are obtained as the crude product, andthis solid is purified by means of digestion with 50 ml of n-hexane.12.65 g of the desired title compound are obtained as a brown solid ofmelting point 110-111° C.

Example H41

3-(3-Fluoro-5-chloro-2-pyridyl)-5-ethoxycarbonyl-1-methyl-[1H]-pyrazole

5.0 g of 3-(3-fluoro-5-chloro-2-pyridyl)-5-bromo-1-methyl-[1H]-pyrazole(Example H40) are initially introduced into an autoclave together with7.2 ml of triethylamine, 0.48 g of bis-triphenylphosphinepalladiumdichloride (PdCl₂(PPh₃)₂) and 70 ml of absolute ethanol. 100 bar ofcarbon monoxide are forced in at 22° C. and the mixture is then kept at100° C. for 48 hours. In the meantime, a further 0.48 g ofbis-triphenylphosphinepalladium dichloride is added. The mixture is thencooled to 22° C. and the pressure is released. The resulting reactionmixture is filtered over Hyflo and—after removal of the ethanol—taken upin ethyl acetate. The ethyl acetate phase is washed with dilutehydrochloric acid and then with brine, dried over sodium sulfate,filtered and concentrated in vacuo. 3.17 g of a brown solid areobtained, and this gives, after purification over a silica gel flashcolumn (eluting agent: n-hexane/ethyl acetate 2/1), 2.31 g of thedesired title compound as a pale yellow solid of melting point 117-118°C.

Example H42

3-(3-Fluoro-5-chloro-2-pyridyl)-4-chloro-5-trifluoromethyl-1-methyl-[1H]-pyrazole

8.63 g of3-(3-fluoro-5-chloro-2-pyridyl)-4-chloro-5-carboxy-1-methyl-[1H]-pyrazoleare initially introduced into a fluorinating unit with 27 g of hydrogenfluoride (HF), 16.2 g of sulfur tetrafluoride (SF₄) and 270 ml ofmethylene chloride. This mixture is kept at 80° C. for 5 hours. It isthen cooled to 22° C. and the SF₄ is removed via a gas elimination unit(stream of argon) and the HF is removed under a water pump vacuum. Afteraddition of methylene chloride, the mixture is extracted three timeswith ice-water and the organic phase which has been separated off isdried over sodium sulfate and then concentrated in vacuo together with40 g of silica gel. After application of this silica gel to a flashcolumn, the column is eluted with a mixture of n-hexane/ethyl acetate5/1. 5.48 g of the desired title compound are obtained as a beige solidof melting point 76-78° C.

Example H43

3-(3-Fluoro-5-chloro-2-pyridyl)-4-methyl-5-carboxy-1-methyl-[1H]-pyrazole

6.75 g of3-(3-fluoro-5-chloro-2-pyridyl)-4-methyl-5methoxycarbonyl-1-methyl-[1H]-pyrazoleare suspended in 40 ml of dimethyl sulfoxide. 14.3 ml of a 2 molarsodium hydroxide solution are added dropwise, while cooling occasionallyin an ice-bath (temperature <30° C.). The thick yellow-brown suspensionis stirred at 22° C. for 2 hours. The resulting suspension is thenintroduced into ice-water and the pH is brought to 1 with 2 molarhydrochloric acid. The slurry formed is filtered with suction and thesolid is washed thoroughly with cold water and then dried in vacuo at60° C. 5.97 g of the desired title compound are obtained as a beigesolid of melting point 194-196° C.

Example H44

3-(3-Fluoro5-chloro-2-pyridyl)-4-methyl-5-carbamoyl-1-methyl-[1H]-pyrazole

3.0 g of 3-(3-fluoro-5-chloro-2-pyridyl)-4-methyl-5-carboxyl-1-methyl-[1H]-pyrazole (Example H43) are initially introduced into 25 ml of1,2-dichloroethane, a total of 1.2 ml of thionyl chloride are slowlyadded at 80° C. and the mixture is subsequently stirred at 80° C for 5hours. The resulting mixture is concentrated in vacuo and three times 20ml of carbon tetrachloride are added and in each case the mixture isevaporated to dryness. The resulting acid chloride is initiallyintroduced into 35 ml of tetrahydrofuran, and ammonia gas is passed in,while cooling in an ice-bath. A brown precipitate forms. Stirring iscontinued overnight at 22° C. The resulting suspension is thenintroduced into five times the volume of ice-water. After briefsubsequent stirring, the solid is filtered off with suction, washed withcold water and dried in vacuo at 60° C. 2.0 g of the desired titlecompound are obtained as a brown solid of melting point 201-204° C. inthis manner.

Example H45

3-(3-Fluoro-5-chloro-2-pyridyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole

1.82 g of3-(3-fluoro-5-chloro-2-pyridyl)-4-methyl-5-carbamoyl-1-methyl-[1H]-pyrazole(Example H44) are suspended in 20 ml of dioxane. First 1.65 ml ofpyridine and then 1.44 ml of trifluoroacetic anhydride are added, whilecooling in an ice-bath. 5 minutes later, the cooling bath is removed andthe mixture is stirred at 22° C. for 1 hour. The brown-red solution isdiluted with diethyl ether and washed with one molar hydrochloric acidand then with brine. After drying over sodium sulfate and filtering, thefiltrate is concentrated directly together with twice the amount ofsilica gel. After application of this silica gel to a flash column, thecolumn is eluted with n-hexane/ethyl acetate 4/1. 1.60 g of the desiredtitle compound are obtained as a beige solid of melting point 144-146°C.

Example H46

3-(3-Fluoro-5-chloro-2-pyridyl)-4-iodo-5-difluoromethoxy-1-methyl-[1H]-pyrazole

3.0 g of3-(3-fluoro-5-chloro-2-pyridyl)-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H15) are dissolved in 30 ml of methylene chloride, and 1.83 gof silver(I) nitrite and 3.02 g of iodine are then added. The mixture isstirred overnight at 22° C. It is then diluted with diethyl ether andextracted successively with aqueous sodium metabisulfite solution andbrine. After drying of the organic phase over sodium sulfate andfiltration, the filtrate is concentrated in vacuo together with twicethe amount of silica gel. After application of this silica gel to aflash column, the column is eluted with n-hexane/ethyl acetate (3/1).3.97 g of the desired title compound are obtained as a beige solid ofmelting point 77-78° C. in this manner.

Example H47

3-(3-Fluoro-5-chloro-2-pyridyl)-4-nitro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

4.0 g of3-(3-fluoro-5chloro-2-pyridyl)-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example HIS) are initially introduced into 30 ml of methylene chloride.3.83 g of nitronium tetrafluoroborate are added, while stirring andcooling in an ice-bath, and the mixture is subsequently stirredovernight at 22° C. The following day, it is poured onto water, andethyl acetate is added. After extraction by shaking and separation ofthe phases, the organic phase is washed with dilute bicarbonate solutionand brine, dried over sodium sulfate, filtered and concentrated invacuo. 4.35 g of the desired title compound are obtained as a brownsolid of melting point 108-109° C.

Example H48

3-(3-Fluoro-5-chloro-2-pyridyl)-4-amino-5difluoromethoxy-1-methyl-[1H]-pyrazole

4.2 g of3-(3-fluoro-5-chloro-2-pyridyl)-4-nitro-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H47) are initially introduced into the reaction vessel togetherwith 40 ml of tetrahydrofuran, and 5.8 g of Raney nickel in ethanol areadded. Hydrogenation is carried out under normal pressure and at atemperature of 30-35° C. After uptake of 728 ml of hydrogen, thehydrogenation is interrupted and the reaction mixture is filtered overHyflo. After removal of the solvent in vacuo, 3.15 g of the desiredtitle compound are obtained as a brown solid of melting point 92-94° C.

Example H49

3-(3-Fluoro-5chloro-2-pyridyl)-4-(2-chloropropionamido-5-difluoromethoxy-1-methyl-[1H]-pyrazole

1.0 g of3-(3-fluoro-5-chloro-2-pyridyl)-4-amino-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H148) is initially introduced into 4 ml of pyridine. 0.46 g ofracemic 2-chloropropionyl chloride in 4 ml of methylene chloride isadded dropwise over 30 minutes, while stirring and cooling in anice-bath, and the mixture is then subsequently stirred at 22° C. for 2hours. The reaction mixture is taken up in ethyl acetate and washed withdilute hydrochloric acid and then with brine. After drying over sodiumsulfate and filtering, the filtrate is concentrated in vacuo and theresidue is then purified over a silica gel flash column (eluting agent:toluene/ethyl acetate 10/1). 0.98 g of the desired title compound isobtained as a white solid of melting point 153-154° C.

Example H50

3-(3Fluoro-5-chloro-6-amino-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

1.84 g of3-(3-fluoro-5-chloro-6-aminocarbonyl-oxymethyl-2-pyridyl)4chloro-s-difluoromethoxy-1-methyl-[1H]-pyrazole are initially introduced into 35 ml of N-methylpyrrolidonetogether with 0.66 g of potassium carbonate. A preheated oilbath of 150°C. is then applied and the mixture is heated overnight at thistemperature. The following day, the reaction mixture is cooled to 22°C., poured onto ice-water and then extracted with diethyl ether. Theether phase is washed with brine and dried over sodium sulfate, fifteredand concentrated in vacuo together with twice the amount of silica gel.After application of this silica gel to a flash column, the column iseluted with a mixture of n-hexane/ethyl acetate 1/1. 0.67 g of thedesired title compound is obtained as a yellow solid.

TLC analysis: silica gel 60 F₂₅₄; eluting agent: n-hexane/ethyl acetate1/1: Rf value of the product: 0.33.

Example H51

3-(3-Fluoro-5-chloro-6-isopropylthio-2-pyridyl)-4-chloro-5difluoromethoxy-1-methyl-[1H]-pyrazole

0.79 g3-(3-fluoro-5-chloro-2-pyridyl-N-oxide)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H19) is initially introduced into 15 ml of benzene. Half of thebenzene is distilled off. The mixture is cooled to 5° C. in an ice-bath,while stirring, 0.22 ml of dimethylcarbamoyl chloride is added dropwiseand the mixture is subsequently stirred at a temperature below 5° C. for30 minutes. Cooling in the ice-bath is continued, and 0.67 ml oftriethylamine and 0.34 ml of 2-propanethiol are added. The mixture isthen stirred overnight, while heating under reflux. After cooling in anice-bath, 0.15 ml of dimethylcarbamoyl chloride and, 10 minutes later,0.50 ml of triethylamine and 0.23 ml of 2-propanethiol are added. Themixture is then again boiled at the reflux temperature overnight. Afterdiluting with diethyl ether, the mixture is washed successively withdilute hydrochloric acid, water, dilute sodium bicarbonate solution andbrine. After drying over sodium sulfate and filtering, the filtrate isconcentrated in vacuo and the residue is purified over a silica gelflash column (eluting agent: toluenelethyl acetate 30/1). 0.22 g of thedesired title compound is obtained as a colourless oil, which thencrystallizes out (melting point 63-64° C.).

Example H52

3-Fluoro-5-chloro-2-f(2-tert-butoxycarbonyl)-protanoylo-pyridine

32.3 g of diisopropylamine are initially introduced into 200 ml oftetrahydrofuran, and 200 ml of a 1.6 molar solution of n-butyllithium inhexane are added dropwise, while cooling with a carbon dioxide(CO₂)/acetone cooling bath. Thereafter, 49.2 ml of tert-butyl propionateare added dropwise at about −75° C. and the mixture is subsequentlystirred at this temperature for 45 minutes. Finally, a solution of 32.6g of ethyl 3-fluoro-5-chloro-2-pyridinecarboxylate (Example H1) in 40 mlof tetrahydrofuran (THF) is then added dropwise at about −75° C. and themixture is subsequently stirred at this temperature for 1 hour.Thereafter, the mixture is diluted with 250 ml of tert-butyl methylether, and a mixture of 100 ml of water and 200 ml of acetic acid isadded. After separation of the phases, the aqueous phase is extractedagain with tert-butyl methyl ether and the combined organic phases arethen washed with water. After drying over magnesium sulfate, the mixtureis filtered and the filtrate is concentrated to dryness in vacuo. 51 gof an oil are obtained as the crude product.

TLC analysis: silica gel 60 F₂₅₄; eluting agent: n-hexane/ethyl acetate3/1 (UV):

Rf value of the starting material: 0.46;

Rf value of the product: 0.63.

Example H53

3-Fluoro-5-chloro-2-(2-carboxypropanoyl)-pyridine

25.5 g of the crude product3-fluoro-5-chloro-2-[(2-tert-butoxycarbonyl)-propanoyl]-pyridine(Example H52) are added dropwise to 30 ml of a 33% solution of hydrogenbromide (HBr) in glacial acetic acid, a suspension being formed. Thissuspension is subsequently stirred for 90 minutes. The mixture is thenintroduced into 300 ml of ice-water and the precipitate formed isfiltered off with suction, washed with water and dried. 15.9 g of thedesired title compound are obtained as a solid of melting point 101-102°C.

Example H54

3-Fluoro-5chloro-2-(2-chloropropanoyl)-pyridine

20.8 g of 3-fluoro-5-chloro 2-(2-carboxypropanoyl)-pyridine (ExampleH53) are initially introduced into 125 ml of glacial acetic acid. 6.3 gof chlorine gas are passed into the solution in the course of 1 hour andthe mixture is then poured onto 700 ml of water and extracted withtert-butyl methyl ether. The ether phase is washed with water and driedover magnesium sulfate, filtered and evaporated in vacuo.

The resulting crude product is dissolved in 180 ml of tert-butyl methylether, and 45 g of silica gel are added. The mixture is stirred for 30minutes, and initially observed evolution of gas ceasing. The silica gelis then filtered off and rinsed and the combined ether phases areconcentrated in vacuo. The resulting crude product (20.1 g of an oil) ispurified over a silica gel flash column (eluting agent: n-hexane/ethylacetate 4/1). 17.0 g of the desired title compound are obtained as asolid of melting point 29-32° C.

Example H55

5-(5-Chloro-3-fluoro-2-pyridyl)-3,6-dimethyl-3,6-dihydro-[1,3,4]-thiadiazine-thione

19.1 ml of a 4 molar sodium hydroxide solution and 3.5 g ofmethylhydrazine are initially introduced into 76 ml of ethanol. 4.5 mlof carbon disulfide are added dropwise whilst stirring at a temperaturebelow 5° C. and the mixture is subsequently stirred for 30 minutes. 17.0g of 3-fluoro-5-chloro-2-(2-chloropropanoyl)-pyridine (Example H54) arethen added in the course of 15 minutes at a temperature below 5° C.Thereafter, the temperature is allowed to rise to 22° C. and thereaction mixture is subsequently stirred for 30 minutes. TLC analysis(silica gel 60 F₂₅₄; eluting agent: n-hexane/ethyl acetate 5/1 (UV)) ofa worked-up sample shows that at this point in time no further startingmaterial is present. 2.5 ml of a concentrated hydrochloric acid solutionare then added dropwise, a yellow precipitate being formed. The mixtureis stirred for 1 hour and then poured onto water and extracted withtert-butyl methyl ether. The ether phase is washed with water, driedover magnesium sulfate, filtered and concentrated in vacuo. 20.3 g ofthe desired title compound are obtained as a solid of melting point107-112° C. in this manner.

Example H56

3-(3-Fluoro-5-chloro-2-pyridyl)-4-methyl-5-methylmercapto-1-methyl-[1H]-pyrazole

21.6 g of5-(5-chloro-3-fluoro-2-pyridyl)-3,6-dimethyl-3,6-dihydro-[1,3,4]-thiadiazine-thione(Example H55) are initially introduced into 70 ml of tert-butanol. 19.1g of triphenylphosphine are then added and the mixture is stirred at atemperature of 65° C. for about 15 minutes, a clear solution beingformed. After cooling to 22° C., a suspension is again formed, to which8.2 g of potassium tert-butylate are added in portions at a temperaturebelow 40° C. (cooling in an ice-bath). The mixture is then subsequentlystirred overnight and thereafter poured onto 600 ml of water, stirred,filtered with suction and washed, and the aqueous phase is extractedthoroughly with tert-butyl methyl ether. The aqueous phase is renderedstrongly acid with concentrated hydrochloric acid and extracted withtert-butyl methyl ether. The ether phase is washed with water, driedover magnesium sulfate, filtered and concentrated in vacuo. 6.8 g of acrude intermediate are obtained in this manner.

1.9 g of this crude product are dissolved in 10 ml of DMF, and 2.2 g ofpotassium carbonate are added. Thereafter, 0.5 ml of methyl iodide in 2ml of DMF is added dropwise under a slightly exothermic reaction. Themixture is then subsequently stirred at 22° C. for 5 hours andthereafter poured onto 120 ml of ice-water and extracted with diethylether. The ether phase is washed with water, dried over magnesiumsulfate, filtered and concentrated in vacuo. The residue (1.8 g of anoil) is purified over a silica gel flash column (eluting agent:n-hexane/ethyl acetate 2/1. 1.3 g of the desired title compound areobtained as a solid of melting point of 61-64° C.

Example H57

3-(3-Fluoro-5-chloro-2-pyridyl)-4-methyl-5-methylsulfoxy-1-methyl-[1H]-pyrazoleand3-(3-fluoro-5-chloro-2-pyridyl)-4-methyl-5-methylsulfonyl-1-methyl-[1H]-pyrazole

2.1 g of3-(3-fluoro-5-chloro-2-pyridyl)-4-methyl-5-methylmercapto-1-methyl-[1H]-pyrazole(Example H56) are dissolved in 40 ml of methylene chloride, and a totalof 2.84 g of 70% meta-chloroperbenzoic acid are added in portions. Themixture is then stirred at 22° C. for 4 hours. It is subsequentlystirred with one molar sodium bicarbonate solution for 30 minutes. Theorganic phase which has been separated off is washed with water, driedover magnesium sulfate, filtered and concentrated in vacuo. 1.7 g of asolid are obtained, and this is purified over a silica gel flash column(eluting agent: n-hexane/ethyl acetate 1/1). 0.80 g of the desiredsulfone of melting point 145-147° C. and 0.70 g of the desired sulfoxideof meting point 112-114° C. are obtained in this manner.

Example H58

3-(3-Fluoro-5chloro-6-(1-hydroxy-2-propyn-3-yl)-2-pyridyl)4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

2.0 of3-(3-fluoro-5,6-dichloro-2-pyridyl)-4-chloro-5difluoromethoxy-1-methyl-[1H]-pyrazole(Example H21) are initially introduced into 15 ml of triethylamine, and0.37 ml of propargyl alcohol is added. The mixture is then evacuated andgassed with argon 3 times under a partial water pump vacuum. Thereafter,0.03 g of copper(I) iodide and 0.12 g ofbis-triphenylphosphine-palladium dichloride (PdCl₂(PPH₃)₂) are added andthe mixture is stirred overnight at 67° C. under argon. The followingday, after cooling to 22° C., 0.20 ml of propargyl alcohol, 0.03 g ofcopper(l) iodide and 0.12 g of PdCl₂(PPH₃)₂ are added. The mixture isthen stirred at 67° C. for 6 hours. After cooling to 22° C., ethylacetate is added and the mixture is washed successively with dilutehydrochloric acid, water and brine. After drying over sodium sulfate,filtration and concentration in vacuo, the residue is purified over asilica gel flash column (eluting agent: n-hexane/ethyl acetate 1/1).0.97 g of the desired title compound is obtained as a yellow oil whichgradually crystallizes; melting point 92-94° C.

Example H59

3-(3-Fluoro-5-chloro-6-(N-propargl-N-ethylsulfonyl)-amino-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

0.81 g of3-(3-fluoro-5-chloro-6-amino-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H50) is dissolved in 10 ml of methylene chloride. 0.93 ml oftriethylamine and then 0.54 ml of ethanesulfonyl chloride (CH₃CH₂SO₂Cl)are added, while stirring and cooling in an ice-bath, and the mixture issubsequently stirred at 22° C. for 48 hours. Diethyl ether is added tothe reaction mixture and the mixture is washed with dilute hydrochloricacid and then with brine. After drying over sodium sulfate, filteringand concentrating in vacuo, 1.0 g of an intermediate product isobtained, and this is dissolved in 10 ml of dioxane. 2.0 ml of a 2 molaraqueous sodium hydroxide solution are added dropwise, while cooling inan ice-bath and stirring, and the mixture is subsequently stirred at 22°C. for 1.5 hours. It is then diluted with diethyl ether and renderedacid with hydrochloric acid. After extraction by shaking and separationof the phases, the ether phase is washed with brine, dried over sodiumsulfate, filtered and concentrated in vacuo. The intermediate obtainedin this manner is dissolved in 20 ml of N-methylpyrrolidone (NMP) andthe solution is stirred and cooled in an ice-bath. 2.0 g of potassiumcarbonate are then added, and 0.45 ml of propargyl bromide is addeddropwise. The mixture is subsequently stirred, with the ice-baththawing, and is then partitioned between ice-water and diethyl ether.After extraction by shaking and separation of the phases, the etherphase is washed with brine, dried over sodium sulfate, fiftered andconcentrated in vacuo together with twice the amount of silica gel.After application of the silica gel to a flash column, the column iseluted with n-hexane/ethyl acetate 2/1). 0.34 g of the desired titlecompound is obtained as a brown-yellow solid of melting point 138-139°C.

Example H60

3-(3-Fluoro-5-chloro-6-carbamoylmethylenoxy-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole

3.0 g of3-(3-fluoro-5-chloro-6-hydroxy-2-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole(Example H30) are initially introduced into 30 ml of N-methylpyrrolidone(NMP) together with 2.53 g of potassium carbonate, and 0.96 g ofchloroacetamide is then added. The mixture is stirred overnight at 50°C. After cooling to 22° C., it is then poured onto ice-water and alittle diethyl ether is added. The slurry formed is filtered withsuction and the solid is washed successively with water, diethyl etherand n-hexane. After drying in vacuo at 50° C., 2.35 g of the desiredtitle compound are isolated as a beige solid.

¹H-NMR (CDCl₃): 7.64 ppm (d, 1H); 6.72 ppm (t, 1H); 6.50 ppm (broad,1H); 5.60 ppm (broad, 1H); 4.6 ppm (s, 2H); 3.87 ppm (s, 3H).

Example H61

3-(3-Fluoro-5-chloro-2-pyridyl)-5-(2.2.2-trifluoroethoxy)-1-methyl-[1H]-pyrazole

3.0 g of3-(3-fluoro-5-chloro-2-pyridyl)-5-hydroxy-1-methyl-[1H]-pyrazole(Example H14) are initially introduced into 30 ml of N-methylpyrrolidone(NMP) together with 3.64 g of potassium carbonate, and 3.49 g of2,2,2-trifluoro-ethanol 4-methylbenzenesulfonate are added. 0.3 g ofsodium iodide is then added and the mixture is stirred overnight at 80°C. It is then cooled to 22° C. and partitioned between dilutehydrochloric acid and diethyl ether. After extraction by shaking andseparation of the phases, the ether phase is washed with brine, filteredand concentrated in vacuo together with twice the amount of silica gel.After application of the silica gel to a flash column, the column iseluted with n-hexane/ethyl acetate 2/1. 2.68 g of the desired titlecompound are obtained as a yellow solid of melting point 72-73° C.

The compounds listed in the following tables can also be prepared in ananalogous manner.

In the following tables 1 to 4, certain structures I_(n), II₁-II₁₃,III₁-III₉, IV₁, IV₂, V₁ or V₂, for example I_(n) to I₃₄ in Table 1 orI₁₀₇ to I136; I₁₄₉-I₁₅₆; II₁-II₁₃; III₁-III₉; IV₁, IV₂; V₁ and V₂ inTable 4, with the same substituent variations, for example R₁₁ and R₁₃in Table 1 or R₁₁, R₁₂ and R₁₃ in Table 4, are combined forsimplification.

In the tables mentioned, all the structures I_(n) or II₁-II₁₂,III₁-III₉, IV₁, IV₂, V₁ or V₂, where for Table 1 n=1 to 34, mentioned inthe heading of the tables should thus be combined with the definitionsgiven in the tables. For example, in Table 1, I_(n).001 discloses eachof the 34 specific compounds I₁.001, I₂.001, I₃.001, I₄.001, I₅.001,I₆.001, I₇.001, I₈.001 and so on up to I₃₄.001, in which in each caseR₁₁ and R₁₃ are fluorine.

TABLE 1 Compounds of the formulae I₁ to I₃₄

Comp. No. I_(n) n = 1-34 R₁₁ R₁₃ 001 F F 002 F H 003 F Cl 004 F NH₂ 005F OH 006 F SH 007 F Br 008 F I 009 F CN 010 F SO₂Cl 011 F NH(CH₃) 012 FN(CH₂CH₃)₂ 013 F NH(COCH₃) 014 F NH(CH₂CH═CH₂) 015 F N(CH₃)(CH₂C≡CH) 016F N(SO₂CH₃)₂ 017 F NH(SO₂CH₂CH₃) 018 F N(CH₂CH═CH₂)(SO₂CH₂CH₃) 019 FN(CH₂C≡CH)(SO₂CH(CH₃)₂) 020 F N(CH₂CF₃)(CHO) 021 F NH(CH₂C₆H₅) 022 FOCH₃ 023 F OCH₂CH₃ 024 F OCH(CH₃)₂ 025 F OCH(CH₃)CH₂CH₂CH₃ 026 FOCH₂CH═CH₂ 027 F OCH(CH₃)CH═CH₂ 028 F OCH₂C≡CH 029 F OCH(CH₃)C≡CH 030 FOCH(cyclopentyl)₂ 031 F OCH₂(C₆H₅) 032 F OCH₂(2-F—C₆H₅) 033 FOCH(CH₃)(4-CH₃—C₆H₅) 034 F OC₆H₅ 035 F O(4-pyrimidyl) 036 F OCH₂CH₂Cl037 F OCH₂CH═CHCl 038 F OCH₂CH₂OH 039 F OCH₂OCH₃ 040 F OCH₂CH₂OCH₂CH₃041 F OCH₂CH₂OCH₂CH₂OCH₂CH₃ 042 F OCH(CH₃)CH₂OCH₂CH═CH₂ 043 F OCOCH₃ 044F OCOOCH₃ 045 F OCOCH₂C₆H₅ 046 F OCH₂SCH₃ 047 F OCH₂CH₂SCH₂CH₃ 048 FOCH₂COOH 049 F OCH(CH₃)COOH 050 F (R)—OCH(CH₃)COOH 051 F(S)—OCH(CH₃)COOH 052 F OCH₂COOCH₂CH₃ 053 F OCH(CH₃)COOCH₃ 054 FOCH(CH₃)COOCH₂CH═CH₂ 055 F OCH(CH₃)COOCH₂(C₆H₅) 056 F OCH(CH₃)CH₂COOH057 F OCH(CH₃)CH₂COOCH₂CH₃ 058 F OCH₂COSCH₃ 059 F OCH(CH₃)COSCH₂CH₃ 060F OCH(CH₃)COSCH(CH₃)₂ 061 F OCH₂CONH₂ 062 F OCH₂CON(CH₂CH₃)₂ 063 FOCH(CH₃)CON(CH₃)₂ 064 F OCH(CH₃)CONH(CH₂CH═CH₂) 065 FOCH(CH₃)CON(CH₃)(CH₂C≡CH) 066 F OCH(CH₃)CON(CH₂C₆H₅)₂ 067 FOCH(CH₃)CON(CH₃)(C₆H₅) 068 F OCH₂COOCH₂CH₂SCH₃ 069 F OCH(CH(CH₃)₂)COOH070 F OCH(CH₃)COOCH₂CH₂OCH₂CH₃ 071 F OCH(C₆H₅)COOH 072 F(R)—OCH(C₆H₅)COOH 073 F (S)—OCH(C₆H₅)COOH 074 F OCH(C₆H₅)COOCH₃ 075 FOCH(C₆H₅)COOCH(CH₃)C≡CH 076 F OCH(C₆H₅)COOCH₂C₆H₅ 077 FOCH(C₆H₅)COSCH(CH₃)₂ 078 F OCH(C₆H₅)CONH₂ 079 F OCH(C₆H₅)CONH(CH₂C≡CH)080 F OCH(C₆H₅)CON(CH₂CH═CH₂)₂ 081 F OCH(C₆H₅)CON(CH₃)CH₂C₆H₅ 082 FOCH(C₆H₅)CONH(CH₂(2-F—C₆H₅)) 083 F OCH(C₆H₅)CONH(cyclopropyl) 084 FOCH₂CH₂COOH 085 F OCH₂CH₂COOCH₂CH₃ 086 F OCH(CH₃)CH₂COOH 087 F SCH₃ 088F SCH(CH₃)₂ 089 F SCH₂CH═CH₂ 090 F SCH₂C₆H₅ 091 F SCH₂CH₂OCH₃ 092 FSC₆H₅ 093 F SCH₂COOH 094 F SCH₂COOCH₂C₆H₅ 095 F SCH(CH₃)COOH 096 FSCH(CH₃)COOCH₂CH₃ 097 F SCH(CH₃)COOCH₂CH═CH₂ 098 F SCH(CH₃)COSCH₃ 099 FSCH(CH₃)CON(CH₃)₂ 100 F SCH(CH₃)CONH(CH₂CH═CH₂) 101 F SOCH₂CH₃ 102 FSO₂CH₃ 103 F SO₂NH₂ 104 F SO₂N(CH₃)₂ 105 F SO₂N(CH₂CH₃)₂ 106 FSO₂N(CH₃)(CH₂(4-CH₃—C₆H₅) 107 F SO₂NHCH₂CH₂OCH₃ 108 F SCOOCH₃ 109 FSCON(CH₃)₂ 110 F SCONHCH₂CH═CH₂ 111 F SCOOCH₂CHCH₂ 112 FSCON(CH₂CH₃)COCF₃ 113 F CHO 114 F COCH₃ 115 F COOCH₂CH₃ 116 F COOCH₂C₆H₅117 F COCl 118 F COCH₂CH₂Cl 119 F COOH 120 F COOCH₃ 121 F COOCH₂CH₃ 122F COOCH(CH₃)₂ 123 F COOCH₂CH═CH₂ 124 F COO(CH₂)₅CH₃ 125 FCOOCH(CH₃)CH═CH₂ 126 F COOCH₂(2-F—C₆H₅) 127 F COOC₆H₅ 128 FCOOCH₂CH₂OCH₂CH₃ 129 F COOCH(CH₃)CH₂SCH₃ 130 F COO(oxetanyl) 131 FCOOCH₂(oxiranyl) 132 F COO(cylopentyl) 133 F COSCH₃ 134 F COSCH(CH₃)₂135 F COSCH₂C₆H₅ 136 F CONH₂ 137 F CONH(CH₂CH═CH₂) 138 F CONHCH₂C₆H₅ 139F CON(CH₂CH═CH₂)₂ 140 F CON(CH₃)OCH₃ 141 F COOCH₂CH₂COOH 142 FCOOCH(CH₃)COOCH₃ 143 F COOCH(CH₃)COOCH₂C₆H₅ 144 F COOCH(CH₃)CH₂COOCH₂CH₃145 F (S)—COOCH(CH₃)CH₂COOCH₂CH═CH₂ 146 F (R)—COOCH(CH₃)CH₂COOCH₂CH═CH₂147 F COOCH(CH₃)CH₂CONHCH₂CH₃ 148 F COOCH(CH₃)CH₂CON(CH₃)₂ 149 FCOOCH(CH₃)CH₂COSCH₂CH₃ 150 F COOCH(CH₃)CH₂COOCH₂CH═CH₂ 151 FCOOC(CH₃)₂COCH₃ 152 F COOC(CH₃)₂COOH 153 F COOC(CH₃)₂COOCH₃ 154 FCOOC(CH₃)₂COOCH₂CH₃ 155 F COOC(CH₃)₂COOCH(CH₃)₂ 156 FCOOC(CH₃)₂COO(CH₂)₄CH₃ 157 F COOC(CH₃)₂COOCH₂C₆H₅ 158 FCOOC(CH₃)₂COOCH₂(2-F—C₆H₅) 159 F COOC(CH₃)₂COOCH₂CH═CH₂ 160 FCOOC(CH₃)₂COOCH(CH₃)CH—CH₂ 161 F COOC(CH₃)₂COOCH₂C≡CH 162 FCOO(CH₃)₂COOCH₂CH₂OCH₂CH₃ 163 F COOC(CH₃)₂COSCH₃ 164 FCOOC(CH₃)₂COSCH(CH₃)₂ 165 F COOC(CH₃)₂COSCH₂C₆H₅ 168 F COOC(CH₃)₂CONH₂167 F COOC(CH₃)₂CONHCH₂CH═CH₂ 168 F COOC(CH₃)₂CON(CH₂CH₃)₂ 169 FCOOC(CH₃)₂CON(CH₃)CH₂CH₂OCH₃ 170 F COSCH(CH₃)COOH 171 F COSCH(CH₃)COOCH₃172 F COSCH(CH₃)CONHCH₂CH═CH₂ 173 F CON(CH₃)CH₂COOH 174 FCON(CH₃)C(CH₃)₂COOCH₂CH₃ 175 F CON(CH₃)OCH₂COOCH₃ 176 F CON(CH₃)OH 177 FCH₃ 178 F CH₂CH₃ 179 F CH(OH)CH₃ 180 F CH(OCH₂CH═CH₂)CH₃ 181 F CH₂Cl 182F CH₂OH 183 F CH₂OCOCH₃ 184 F CHClCH₃ 185 F CH₂CH₂CF₃ 186 F CH═CHCF₃ 187F OH₂CH═CH₂ 188 F CH═CHCH₃ 189 F C≡CH 190 F CCCH₂OH 191 F CH₂CHClCOOH192 F (R)—CH₂CHClCOOH 193 F (S)—CH₂CHClCOOH 194 F CH₂CH(CH₃)COOH 195 FCH₂CH(CH₃)COOCH₂CH₃ 196 F CH(Cl)CH₂COOCH₃ 197 F CH(Cl)C(Cl)₂COOH 198 FCH(Cl)CH(Cl)COOCH₂CH₃ 199 F CH₂CH(CH₃)COOH 200 F CH₂CH(CH₃)COCH₂CH═CH₂201 F CH₂CH(CH₃)CONH(CH₂CH═CH₂) 202 F CH₂CH(CH₃)CON(CH₃)₂ 203 FCH₂CH(CH₃)COSCH(CH₃)₂ 204 F CH₂CHClCOOC(CH₃)₃ 205 F CH₂CHClCOOCH₃ 206 FCH₂CHClCOOCH₂CH₃ 207 F CH₂CHClCOOCH(CH₃)₂ 208 F CH₂CHClCOOCH₂CH═CH₂ 209F CH₂CHClCOOCH₂C₆H₅ 210 F CH₂CHClCOSCH₃ 211 F CH₂CHClCOSCH(CH₃)₂ 212 FCH₂CHClCOSCH₂C₆H₅) 213 F CH₂CHClCONH₂ 214 F CH₂CHClCONH(CH₂CH═CH₂) 215 FCH₂CHClCON(CH₂CH₃)₂ 216 F CH₂CHClCONH(CH₂C₆H₅) 217 FCH₂CHClCON(CH₃)CH₂C₆H₅ 218 F CH═CHCOOH 219 F (E)-CH═CHCOOH 220 F(Z)-CH═CHCOOH 221 F CH═CHCOOCH₃ 222 F CH═CHCOOCH₂C₆H₅ 223 F CH═CHCONH₂224 F CH═CHCONH(CH₂CH═CH₂) 225 F CH═C(Cl)COOH 226 F CH═C(Cl)CONH₂ 227 FCH═C(Cl)CONH(CH₂CH₃) 228 F CH═C(Cl)CON(CH₂CH₃)₂ 229 FCH═C(Cl)CONH(CH₂C₆H₅) 230 F CH═C(Cl)COSCH₃ 231 F CH═C(Cl)COSCH(CH₃)₂ 232F CH═C(CH₃)COOH 233 F CH═C(CH₃)CONH(CH₂CH═CH₂) 234 F CH═C(CH₃)CON(CH₃)₂235 F CH═C(CH₃)COSCH₂CH₃ 236 F CH═C(CN)COOH 237 F CH═C(CN)COOC(CH₃)₃ 238F CH═C(CN)CON(CH₂CH═CH₂)₂ 239 F CH═C(COOH)₂ 240 F CH═C(C₆H₅)COOH 241 FCH═CHCH₂OH 242 Cl F 243 Cl H 244 Cl Cl 245 Cl NH₂ 246 Cl OH 247 Cl SH248 Cl Br 249 Cl I 250 Cl CN 251 Cl SO₂Cl 252 Cl NH(CH₃) 253 ClN(CH₂CH₃)₂ 254 Cl NH(COCH₃) 255 Cl NH(CH₂CH═CH₂) 256 Cl N(CH₃)(CH₂C≡CH)257 Cl N(SO₂CH₃)₂ 258 Cl NH(SO₂CH₂CH₃) 259 Cl N(CH₂CH═CH₂)(SO₂CH₂CH₃)260 Cl N(CH₂C≡CH)(SO₂CH(CH₃)₂) 261 Cl N(CH₂CF₃)(CHO) 262 Cl NH(CH₂C₆H₅)263 Cl OCH₃ 264 Cl OCH₂CH₃ 265 Cl OCH(CH₃)₂ 266 Cl OCH(CH₃)CH₂CH₂CH₃ 267Cl OCH₂CH═CH₂ 268 Cl OCH(CH₃)CH═CH₂ 269 Cl OCH₂C≡CH 270 Cl OCH(CH₃)C≡CH271 Cl OCH(cyclopentyl) 272 Cl OCH₂(C₆H₅) 273 Cl OCH₂(2-F—C₆H₅) 274 ClOCH(CH₃)(4-CH₃—C₆H₅) 275 Cl OC₆H₅ 276 Cl O(4-pyrimidyl) 277 Cl OCH₂CH₂Cl278 Cl OCH₂CH═CHCl 279 Cl OCH₂CH₂OH 280 Cl OCH₂OCH₃ 281 ClOCH₂CH₂OCH₂CH₃ 282 Cl OCH₂CH₂OCH₂CH₂OCH₂CH₃ 283 Cl OCH(CH₃)CH₂OCH₂CH═CH₂284 Cl OCOCH₃ 285 Cl OCOOCH₃ 286 Cl OCOCH₂C₆H₅ 287 Cl OCH₂SCH₃ 288 ClOCH₂CH₂SCH₂CH₃ 289 Cl OCH₂COOH 290 Cl OCH(CH₃)COOH 291 Cl(R)—OCH(CH₃)COOH 292 Cl (S)—OCH(CH₃)COOH 293 Cl OCH₂COOCH₂CH₃ 294 ClOCH(CH₃)COOCH₃ 295 Cl OCH(CH₃)COOCH₂CH═CH₂ 296 Cl OCH(CH₃)COOCH₂(C₆H₅)297 Cl OCH(CH₃)CH₂COOH 298 Cl OCH(CH₃)CH₂COOCH₂CH₃ 299 Cl OCH₂COSCH₃ 300Cl OCH(CH₃)COSCH₂CH₃ 301 Cl OCH(CH₃)COSCH(CH₃)₂ 302 Cl OCH₂CONH₂ 303 ClOCH₂CON(CH₂CH₃)₂ 304 Cl OCH(CH₃)CON(CH₃)₂ 305 Cl OCH(CH₃)CONH(CH₂CH═CH₂)306 Cl OCH(CH₃)CON(CH₃)(CH₂C≡CH) 307 Cl OCH(CH₃)CON(CH₂C₆H₅)₂ 308 ClOCH(CH₃)CON(CH₃)(C₆H₅) 309 Cl OCH₂COOCH₂CH₂SCH₃ 310 Cl OCH(CH(CH₃)₂)COOH311 Cl OCH(CH₃)COOCH₂CH₂OCH₂CH₃ 312 Cl OCH(C₆H₅)COOH 313 Cl(R)—OCH(C₆H₅)COOH 314 Cl (S)—OCH(C₆H₅)COOH 315 Cl OCH(C₆H₅)COOCH₃ 316 ClOCH(C₆H₅)COOCH(CH₃)C≡CH 317 Cl OCH(C₆H₅)COOCH₂C₆H₅ 318 ClOCH(C₆H₅)COSCH(CH₃)₂ 319 Cl OCH(C₆H₅)CONH₂ 320 Cl OCH(C₆H₅)CONH(CH₂C≡CH)321 Cl OCH(C₆H₅)CON(CH₂CH═CH₂)₂ 322 Cl OCH(C₆H₅)CON(CH₃)CH₂C₆H₅ 323 ClOCH(C₆H₅)CONH(CH₂(2-F—C₆H₅) 324 Cl OCH(C₆H₅)CONH(cyclopropyl) 325 ClOCH₂CH₂COOH 326 Cl OCH₂CH₂COOCH₂CH₃ 327 Cl OCH(CH₃)CH₂COOH 328 Cl SCH₃329 Cl SCH(CH₃)₂ 330 Cl SCH₂CH═CH₂ 331 Cl SCH₂C₆H₅ 332 Cl SCH₂CH₂OCH₃333 Cl SC₆H₅ 334 Cl SCH₂COOH 335 Cl SCH₂COOCH₂C₆H₅ 336 Cl SCH(CH₃)COOH337 Cl SCH(CH₃)COOCH₂CH₃ 338 Cl SCH(CH₃)COOCH₂CH═CH₂ 339 ClSCH(CH₃)COSCH₃ 340 Cl SCH(CH₃)CON(CH₃)₂ 341 Cl SCH(CH₃)CONH(CH₂CH═CH₂)342 Cl SOCH₂CH₃ 343 Cl SO₂CH₃ 344 Cl SO₂NH₂ 345 Cl SO₂N(CH₃)₂ 346 ClSO₂N(CH₂CH₃)₂ 347 Cl SO₂N(CH₃)(CH₂(4-CH₃—C₆H₅) 348 Cl SO₂NHCH₂CH₂OCH₃349 Cl SCOOCH₃ 350 Cl SCON(CH₃)₂ 351 Cl SCONHCH₂CH═CH₂ 352 ClSCOOCH₂CH═CH₂ 353 Cl SCON(CH₂CH₃)COCF₃ 354 Cl CHO 355 Cl COCH₃ 356 ClCOOCH₂CH₃ 357 Cl COOCH₂C₆H₅ 358 Cl COCl 359 Cl COCH₂CH₂Cl 360 Cl COOH361 Cl COOCH₃ 362 Cl COOCH₂CH₃ 363 Cl COOCH(CH₃)₂ 364 Cl COOCH₂CH═CH₂365 Cl COO(CH₂)₅CH₃ 366 Cl COOCH(CH₃)CH═CH₂ 367 Cl COOCH₂(2-F—C₆H₅) 368Cl COOC₆H₅ 369 Cl COOCH₂CH₂OCH₂CH₃ 370 Cl COOCH(CH₃)CH₂SCH₃ 371 ClCOO(oxetanyl) 372 Cl COOCH₂(oxiranyl) 373 Cl COO(cylopentyl) 374 ClCOSCH₃ 375 Cl COSCH(CH₃)₂ 376 Cl COSCH₂C₆H₅ 377 Cl CONH₂ 378 ClCONH(CH₂CH═CH₂) 379 Cl CONHCH₂C₆H₅ 380 Cl CON(CH₂CH═CH₂)₂ 381 ClCON(CH₃)OCH₃ 382 Cl COOCH₂CH₂COOH 383 Cl COOCH(CH₃)COOCH₃ 384 ClCOOCH(CH₃)COOCH₂C₆H₅ 385 Cl COOCH(CH₃)CH₂COOCH₂CH₃ 386 Cl(S)—COOCH(CH₃)CH₂COOCH₂CH═CH₂ 387 Cl (R)—COOCH(CH₃)CH₂COOCH₂CH═CH₂ 388Cl COOCH(CH₃)CH₂CONHCH₂CH₃ 389 Cl COOCH(CH₃)CH₂CON(CH₃)₂ 390 ClCOOCH(CH₃)CH₂COSCH₂CH₃ 391 Cl COOCH(CH₃)CH₂COOCH₂CH═CH₂ 392 ClCOOC(CH₃)₂COCH₃ 393 Cl COOC(CH₃)₂COOH 394 Cl COOC(CH₃)₂COOCH₃ 395 ClCOOC(CH₃)₂COOCH₂CH₃ 396 Cl COOC(CH₃)₂COOCH(CH₃)₂ 397 ClCOOC(CH₃)₂COO(CH₂)₄CH₃ 398 Cl COOC(CH₃)₂COOCH₂C₆H₅ 399 ClCOOC(CH₃)₂COOCH₂(2-F—C₆H₅) 400 Cl COOC(CH₃)₂COOCH₂CH═CH₂ 401 ClCOOC(CH₃)₂COOCH(CH₃)CH═CH₂ 402 Cl COOC(CH₃)₂COOCH₂C≡CH 403 ClCOO(CH₃)₂COOCH₂CH₂OCH₂CH₃ 404 Cl COOC(CH₃)₂COSCH₃ 405 ClCOOC(CH₃)₂COSCH(CH₃)₂ 406 Cl COOC(CH₃)₂COSCH₂C₆H₅ 407 Cl COOC(CH₃)₂CONH₂408 Cl COOC(CH₃)₂CONHCH₂CH═CH₂ 409 Cl COOC(CH₃)₂CON(CH₂CH₃)₂ 410 ClCOOC(CH₃)₂CON(CH₃)CH₂CH₂OCH₃ 411 Cl COSCH(CH₃)COOH 412 ClCOSCH(CH₃)COOCH₃ 413 Cl COSCH(CH₃)CONHCH₂CH═CH₂ 414 Cl CON(CH₃)CH₂COOH415 Cl CON(CH₃)C(CH₃)₂COOCH₂CH₃ 416 Cl CON(CH₃)OCH₂COOCH₃ 417 ClCON(CH₃)OH 418 Cl CH₃ 419 Cl CH₂CH₃ 420 Cl CH(OH)CH₃ 421 ClCH(OCH₂CH═CH₂)CH₃ 422 Cl CH₂Cl 423 Cl CH₂OH 424 Cl CH₂OCOCH₃ 425 ClCHClCH₃ 426 Cl CH₂CH₂CF₃ 427 Cl CH═CHCF₃ 428 Cl CH₂CH═CH₂ 429 ClCH═CH(CH₃) 430 Cl C≡CH 431 Cl C≡CCH₂OH 432 Cl CH₂CHClCOOH 433 Cl(R)—CH₂CHClCOOH 434 Cl (S)—CH₂CHClCOOH 435 Cl CH₂CH(CH₃)COOH 436 ClCH₂CH(CH₃)COOCH₂CH₃ 437 Cl CH(Cl)CH₂COOCH₃ 438 Cl CH(Cl)C(Cl)₂COOH 439Cl CH(Cl)CH(Cl)COOCH₂CH₃ 440 Cl CH₂CH(CH₃)COOH 441 ClCH₂CH(CH₃)COCH₂CH═CH₂ 442 Cl CH₂CH(CH₃)CONH(CH₂CH═CH₂) 443 ClCH₂CH(CH₃)CON(CH₃)₂ 444 Cl CH₂CH(CH₃)COSCH(CH₃)₂ 445 ClCH₂CHClCOOC(CH₃)₃ 446 Cl CH₂CHClCOOCH₃ 447 Cl CH₂CHClCOOCH₂CH₃ 448 ClCH₂CHClCOOCH(CH₃)₂ 449 Cl CH₂CHClCOOCH₂CH═CH₂ 450 Cl CH₂CHClCOOCH₂C₆H₅451 Cl CH₂CHClCOSCH₃ 452 Cl CH₂CHClCOSCH(CH₃)₂ 453 Cl CH₂CHClCOSCH₂C₆H₅454 Cl CH₂CHClCONH₂ 455 Cl CH₂CHClCONH(CH₂CH═CH₂) 456 ClCH₂CHClCON(CH₂CH₃)₂ 457 Cl CH₂CHClCONH(CH₂C₆H₅) 458 ClCH₂CHClCON(CH₃)CH₂C₆H₅ 459 Cl CH═CHCOOH 460 Cl (E)-CH═CHCOOH 461 Cl(Z)-CH═CHCOOH 462 Cl CH═CHCOOCH₃ 463 Cl CH═CHCOOCH₂C₆H₅ 464 ClCH═CHCOONH₂ 465 Cl CH═CHCONH(CH₂CH═CH₂) 466 Cl CH═C(Cl)COOH 467 ClCH═C(Cl)CONH₂ 468 Cl CH═C(Cl)CONH(CH₂CH₃) 469 Cl CH═C(Cl)CON(CH₂CH₃)₂470 Cl CH═C(Cl)CONH(CH₂C₆H₅) 471 Cl CH═C(Cl)COSCH₃ 472 ClCH═C(Cl)COSCH(CH₃)₂ 473 Cl CH═C(CH₃)COOH 474 Cl CH═C(CH₃)CONH(CH₂CH═CH₂)475 Cl CH═C(CH₃)CON(CH₃)₂ 476 Cl CH═C(CH₃)COSCH₂CH₃ 477 Cl CH═C(CN)COOH478 Cl CH═C(CN)COOC(CH₃)₃ 479 Cl CH═C(CN)CON(CH₂CH═CH₂)₂ 480 ClCH═C(COOH)₂ 481 Cl CH═C(C₆H₅)COOH 482 Cl CH═CHCH₂OH 483 H F 484 H H 485H Cl 486 H Br 487 H I 488 H NH₂ 489 H OH 490 H SH 491 H SO₂Cl 492 H CN493 H NH(CH₂C₆H₅) 494 H N(CH₂CH═CH₂)₂ 495 H N(SO₂CH₃)₂ 496 HNH(SO₂CH₂CH₃ 497 H NH(COCH₃) 498 H OCH₃ 499 H OCH₂CH₃ 500 H OCH₂CH═CH₂501 H OCH₂C≡CH 502 H OCH₂C₆H₅ 503 H OCH₂CH₂Cl 504 H OCH₂CH₂OH 505 HOCH₂OCH₃ 506 H OCH₂CH₂OCH₂CH₃ 507 H OCH₂CH₂OCH₂CH₂OCH₃ 508 H OCOCH₃ 509H OCOOCH₃ 510 H OCH₂SCH₃ 511 H OCH₂CH₂SCH₃ 512 H OCH₂COOH 513 HOCH₂COOCH₃ 514 H OCH₂COOCH₂C₆H₅ 515 H OCH₂CONH(CH₃) 516 H OCH(CH₃)COOH517 H OCH(CH₃)COOCH₂CH₃ 518 H OCH(CH₃)COOCH₂CH═CH₂ 519 HOCH(CH₃)COOCH₂C₆H₅ 520 H OCH(CH₃)CONH₂ 521 H OCH(CH₃)CONH(CH₂CH═CH₂) 522H OCH(CH₃)CON(CH₃)₂ 523 H OCH(CH₃)COSCH(CH₃)₂ 524 H OCH(C₆H₅)COOH 525 HOCH(C₆H₅)COOCH₃ 526 H OCH(C₆H₅)COOCH₂CH═CH₂ 527 H OCH(C₆H₅)CONH₂ 528 HOCH(C₆H₅)CONH(CH₂CH₃) 529 H OCH(C₆H₅)CON(CH₃)₂ 530 H OCH(C₆H₅)COSCH₃ 531H OCH(C₆H₅)COSCH(CH₃)₂ 532 H OCH(CH₃)CH₂COOH 533 H OCH(CH₃)CH₂COOCH₂CH₃534 H SCH₃ 535 H SCH(CH₃)₂ 536 H SCH₂C₆H₅ 537 H SCH(CH₃)COOH 538 HSCH(CH₃)COOCH₂CH₃ 539 H SO₂NH₂ 540 H SO₂NH(CH₂CH═CH₂) 541 H SO₂N(CH₃)₂542 H SCOCH₃ 543 H SCOOCH₂CH₃ 544 H CH₂OCOCH₃ 545 H COOH 546 H COCl 547H COOCH₃ 548 H COOCH(CH₃)₂ 549 H COOCH₂C₆H₅ 550 H COSCH(CH₃)₂ 551 HCONH₂ 552 H CONHCH₂C₆H₅ 553 H CON(CH₂CH═CH₂)₂ 554 H CON(CH₃)OCH₃ 555 HCOOCH(CH₃)CH₂COOH 556 H COOCH(CH₃)COOCH₂CH₃ 557 HCOOCH(CH₃)CH₂COOCH₂CH═CH₂ 558 H COOCH(CH₃)CH₂COSCH₂CH₃ 559 HCOOCH(CH₃)CH₂CONH₂ 560 H COOCH(CH₃)CH₂CONH(CH₂CH═CH₂) 561 HCOOCH(CH₃)COOH 562 H COOC(CH₃)₂COOH 563 H COOC(CH₃)₂COOCH₃ 564 HCOOC(CH₃)₂COOCH(CH₃)₂ 565 H COOC(CH₃)₂COOCH₂CH₃ 566 HCOOC(CH₃)₂COOCH₂CH═CH₂ 567 H COOC(CH₃)₂COOCH₂CH₂OCH₂CH₃ 568 HCOOC(CH₃)₂CONH₂ 569 H COOC(CH₃)₂CON(CH₃)₂ 570 HCOOC(CH₃)₂CONH(CH₂CH═CH₂) 571 H COSCH(CH₃)COOH 572 H CON(CH₃)C(CH₃)₂COOH573 H CH₃ 574 H CH₂CH₃ 575 H CH(OH)CH₃ 576 H CH₂Cl 577 H CH₂OH 578 HCH₂OCOCH₃ 579 H CH═CHCF₃ 580 H CH₂CH₂CF₃ 581 H CH₂CH═CH₂ 582 HCH₂CHClCOOH 583 H CH₂CHClCOOCH₂CH₃ 584 H CH₂CHClCOOCH₂C₆H₅ 585 HCH₂CHClCOOCH₂CH═CH₂ 586 H CH₂CHClCOOC(CH₃)₃ 587 H CH₂CHClCOSCH(CH₃)₂ 588H CH₂CHClCONH₂ 589 H CH₂CHClCONH(CH₂CH₃) 590 H CH₂CHClCON(CH₃)₂ 591 HCH(Cl)CH(Cl)COOH 592 H CH₂C(CH₃)ClCOOH 593 H CH₂C(CH₃)ClCOOCH₂CH₃ 594 HCH₂C(CH₃)ClCOSCH₃ 595 H CH₂C(CH₃)ClCONH(CH₂CH═CH₂) 596 HCH₂C(CH₃)ClCON(CH₃)(CH₂CH═CH₂) 597 H CH═CHCOOH 598 H CH═C(CH₃)COOH 599 HCH═C(Cl)COOH 600 H CH═C(CN)COOH 601 H CH═C(CN)COOCH₂CH═CH₂ 602 HCH═C(Cl)COOCH₂CH₃ 603 H CH═C(CH₃)CONH(CH₂CH═CH₂) 604 H CH═C(Cl)COSCH₂CH₃605 H CH═C(Cl)CON(CH₃)₂ 606 CH₃ F 607 CH₃ H 608 CH₃ Cl 609 CH₃ Br 610CH₃ I 611 CH₃ NH₂ 612 CH₃ OH 613 CH₃ SH 614 CH₃ SO₂Cl 615 CH₃ CN 616 CH₃NH(CH₂C₆H₅) 617 CH₃ N(CH₂CH═CH₂)₂ 618 CH₃ N(SO₂CH₃)₂ 619 CH₃NH(SO₂CH₂CH₃ 620 CH₃ NH(COCH₃) 621 CH₃ OCH₃ 622 CH₃ OCH₂CH₃ 623 CH₃OCH₂CH═CH₂ 624 CH₃ OCH₂C≡CH 625 CH₃ OCH₂C₆H₅ 626 CH₃ OCH₂CH₂Cl 627 CH₃OCH₂CH₂OH 628 CH₃ OCH₂OCH₃ 629 CH₃ OCH₂CH₂OCH₂CH₃ 630 CH₃OCH₂CH₂OCH₂CH₂OCH₃ 631 CH₃ OCOCH₃ 632 CH₃ OCOOCH₃ 633 CH₃ OCH₂CH₃ 634CH₃ OCH₂CH₂SCH₃ 635 CH₃ OCH₂COOH 636 CH₃ OCH₂COOCH₃ 637 CH₃OCH₂COOCH₂C₆H₅ 638 CH₃ OCH₂CONH(CH₃) 639 CH₃ OCH(CH₃)COOH 640 CH₃OCH(CH₃)COOCH₂CH₃ 641 CH₃ OCH(CH₃)COOCH₂CH═CH₂ 642 CH₃OCH(CH₃)COOCH₂C₆H₅ 643 CH₃ OCH(CH₃)CONH₂ 644 CH₃ OCH(CH₃)CONH(CH₂CH═CH₂)645 CH₃ OCH(CH₃)CON(CH₃)₂ 646 CH₃ OCH(CH₃)COSCH(CH₃)₂ 647 CH₃OCH(C₆H₅)COOH 648 CH₃ OCH(C₆H₅)COOCH₃ 649 CH₃ OCH(C₆H₅)COOCH₂CH═CH₂ 650CH₃ OCH(C₆H₅)CONH₂ 651 CH₃ OCH(C₆H₅)CONH(CH₂CH₃) 652 CH₃OCH(C₆H₅)CON(CH₃)₂ 653 CH₃ OCH(C₆H₅)COSCH₃ 654 CH₃ OCH(C₆H₅)COSCH(CH₃)₂655 CH₃ OCH(CH₃)CH₂COOH 666 CH₃ OCH(CH₃)CH₂COOCH₂CH₃ 657 CH₃ SCH₃ 658CH₃ SCH(CH₃)₂ 659 CH₃ SCH₂C₆H₅ 660 CH₃ SCH(CH₃)COOH 661 CH₃SCH(CH₃)COOCH₂CH₃ 662 CH₃ SO₂NH₂ 663 CH₃ SO₂NH(CH₂CH═CH₂) 664 CH₃SO₂N(CH₃)₂ 665 CH₃ SCOCH₃ 666 CH₃ SCOOCH₂CH₃ 667 CH₃ CH₂OCOCH₃ 668 CH₃COOH 669 CH₃ COCl 670 CH₃ COOCH₃ 671 CH₃ COOCH(CH₃)₂ 672 CH₃ COOCH₂C₆H₅673 CH₃ COSCH(CH₃)₂ 674 CH₃ CONH₂ 675 CH₃ CONHCH₂C₆H₅ 676 CH₃CON(CH₂CH═CH₂)₂ 677 CH₃ CON(CH₃)OCH₃ 678 CH₃ COOCH(CH₃)CH₂COOH 679 CH₃COOCH(CH₃)COOCH₂CH₃ 680 CH₃ COOCH(CH₃)CH₂COOCH₂CH═CH₂ 681 CH₃COOCH(CH₃)CH₂COSCH₂CH₃ 682 CH₃ COOCH(CH₃)CH₂CONH₂ 683 CH₃COOCH(CH₃)CH₂CONH(CH₂CH═CH₂) 684 CH₃ COOCH(CH₃)COOH 685 CH₃COOC(CH₃)₂COOH 686 CH₃ COOC(CH₃)₂COOCH₃ 687 CH₃ COOC(CH₃)₂COOCH(CH₃)₂688 CH₃ COOC(CH₃)₂COOCH₂CH₃ 689 CH₃ COOC(CH₃)₂COOCH₂CH═CH₂ 690 CH₃COOC(CH₃)₂COOCH₂CH₂OCH₂CH₃ 691 CH₃ COOC(CH₃)₂CONH₂ 692 CH₃COOC(CH₃)₂CON(CH₃)₂ 693 CH₃ COOC(CH₃)₂CONH(CH₂CH═CH₂) 694 CH₃COSCH(CH₃)COOH 695 CH₃ CON(CH₃)C(CH₃)₂COOH 696 CH₃ CH₃ 697 CH₃ CH₂CH₃698 CH₃ CH(OH)CH₃ 699 CH₃ CH₂Cl 700 CH₃ CH₂OH 701 CH₃ CH₂OCOCH₃ 702 CH₃CH═CHCF₃ 703 CH₃ CH₂CH₂CF₃ 704 CH₃ CH₂CH═CH₂ 705 CH₃ CH₂CHClCOOH 706 CH₃CH₂CHClCOOCH₂CH₃ 707 CH₃ CH₂CHClCOOCH₂C₆H₅ 708 CH₃ CH₂CHClCOOCH₂CH═CH₂709 CH₃ CH₂CHC(COOC(CH₃)₃ 710 CH₃ CH₂CHClCOSCH(CH₃)₂ 711 CH₃CH₂CHClCONH₂ 712 CH₃ CH₂CHClCONH(CH₂CH₃) 713 CH₃ CH₂CHClCON(CH₃)₂ 714CH₃ CH(Cl)CH(Cl)COOH 715 CH₃ CH₂C(CH₃)ClCOOH 716 CH₃CH₂C(CH₃)ClCOOCH₂CH₃ 717 CH₃ CH₂C(CH₃)ClCOSCH₃ 718 CH₃CH₂C(CH₃)ClCONH(CH₂CH═CH₂) 719 CH₃ CH₂C(CH₃)ClCON(CH₃)(CH₂CH═CH₂) 720CH₃ CH═CHCOOH 721 CH₃ CH═C(CH₃)COOH 722 CH₃ CH═C(Cl)COOH 723 CH₃CH═C(CN)COOCH₂CH═CH₂ 724 CH₃ CH═C(CN)COOH 725 CH₃ CH═C(Cl)COOCH₂CH₃ 726CH₃ CH═C(CH₃)CONH(CH₂CH═CH₂) 727 CH₃ CH═C(Cl)COSCH₂CH₃ 728 CH₃CH═C(Cl)CON(CH₃)₂ 729 H N-imidazolyl 730 F N-imidazolyl 731 ClN-imidazolyl 732 CH₃ N-imidazolyl 733 H COOCH₂CH₃ 734 CH₃ COOCH₂CH₃ 735F N(CH₃)₂ 736 F OCH₂CH₂OCH₂CH₂OCH₃ 737 F OCH₂COOCH₂CH₃ 738 FOCH(CH₃)COOCH₂CH₃ 739 F OCH₂CH(OH)CH₂OH 740 F CH═CH₂ 741 F COSCH₂CH₃ 742F COO⁻⁺NH₂(CH(CH₃)₂)₂ 743 F COO⁻⁺NH(CH₂CH₂OH)₃ 744 F COO⁻⁺K 745 FOCH₂COOC(CH₃)₃ 746 F OCH₂CH₂C₆H₅ 747 F N(CH₂C≡CH)(SO₂CH₂CH₃) 748 FOCH₂CH₂CH₂CH₃ 749 F OCH(C₆H₅)COOCH₂CH₃ 750 F OCH₂CH₂CH₂COOCH₂CH₃ 751 FCOOCH₂CH(CH₃)CF₃ 752 F COOCH(CH₃)COOCH₂CH₃ 753 F CON(CH₂CH₂CH₃)₂ 754 FCOOCH₂CH₂CH₂CH₂CH₃ 755 F COOCH₂CH₂SCH₂CH₂CH₂CH₃ 756 F COOCH₂CH₂CN 757 FCOOCH₂CH₂SCH(CH₃)₂ 758 F COOCH₂CH₂CH₂C₆H₅ 759 F COOCH(CH₃)CH₂CH₂CH₃ 760F COO(CH₂)₅COOCH₂CH₃ 761 F COOC(CH₃)₃ 762 F OCH₂CH₂CH₃ 763 F OCH₂CH═CHCl764 F CH═C(CH₃)COOCH₂CH₃ 765 F COO-cyclopropyl 766 F COO-cyclohexyl 767F COOCH_(2-cyclopropyl) 768 F COOCH₂C₆H₅ 769 F COOCH₂CH₂OCH₃ 770 FCOOCH₂CH₂CH₃ 771 F COOCH₂CH(CH₃)₂ 772 F COOCH₂CH₂CH₂CH₃ 773 FCOOCH₂CH(CH₃)CH₂CH₃ 774 F COOCH₂(p-Cl—C₆H₄) 775 F COOCH(CH₃)C₆H₄ 776 FCOSCH₂(o-F—C₆H₄) 777 F COSCH(CH₃)CH₂CH₃ 778 F COSCH(CH₃)C₆H₅ 779 FCOSCH₂CH₂CH₃ 780 F COSCH₂CH═CH₂ 781 F CON(CH₂CH═CH₂)CH₂CH₃ 782 FCON(SO₂CH₃)CH₃ 783 F CON(SO₂CH₃)CH₂CH═CH₂ 784 Cl COO-cyclopropyl 785 ClCOO-cyclohexyl 786 Cl COOCH_(2-cyclopropyl) 787 Cl COOCH₂C₆H₅ 788 ClCOOCH₂CH₂OCH₃ 789 Cl COOCH₂CH₂CH₃ 790 Cl COOCH₂CH(CH₃)₂ 791 ClCOOCH₂CH₂CH₂CH₃ 792 Cl COOCH₂CH(CH₃)CH₂CH₃ 793 Cl COOCH₂(p-Cl—C₆H₄) 794Cl COOCH(CH₃)C₆H₅ 795 Cl COOCH(CH₃)C₆H₅ 796 Cl COSCH₂(o-F—C₆H₄) 797 ClCOSCH(CH₃)CH₂CH₃ 798 Cl COSCH(CH₃)C₆H₅ 799 Cl COSCH₂CH₂CH₃ 800 ClCOSCH₂CH═CH₂ 801 Cl CON(CH₂CH═CH₂)CH₂CH₃ 802 Cl CON(SO₂CH₃)CH₃ 803 ClCON(SO₂CH₃)CH₂CH═CH₂ 804 H COOC(CH₃)₂COCl 805 F CH═C(F)COOCH₂CH₃ (E/Z)806 F CH═C(Cl)COOCH₂CH₃ (E/Z) 807 F OCH₂COOCH₂C₆H₅ 808 F OCH₂CN

TABLE 2 Compounds of the formulae I₃₅-I₆₇, I₁₄₇, I₁₄₈

Comp. No. I_(n) n = 35-67, 147, 148 R₃ R₁₁ R₁₃ 001 Cl H H 002 Br H H 003NH₂ H H 004 NH(CH₂CH₃) H H 005 N(CH₂C≡CH)₂ H H 006 N(CH₃)(CH₂CH═CH₂) H H007 NH(CH₂C₆H₅) H H 008

H H 009 NHCOCH₃ H H 010 NHCOCH₂CH₃ H H 011 NHCOCHClCH₃ H H 012 NHCOCH₂ClH H 013 NHCOCHCl₂ H H 014 N(CH₃)COCHCl₂ H H 015 N(CH₂C≡CH)COCHCl₂ H H016 NHCOCF₃ H H 017 N(COCF₃)₂ H H 018 NHCOCF₂CF₃ H H 019 NHCOCClF₂ H H020 NHCOCF₂CF₂CF₃ H H 021 NHCO(2-thienyl) H H 022 NHCO(3-furanyl) H H023 NHCO(3-tetrahydrofuranyl) H H 024 NHCO(2-furanyl) H H 025NHCO(2-tetrahydrofuranyl) H H 026 NHSO₂CH₃ H H 027 N(SO₂CH₃)₂ H H 028NHSO₂CH₂CH₃ H H 029 N(CH₂C≡CH)SO₂CH₂CH₃ H H 030 NHSO₂CF₃ H H 031 Cl Cl H032 Br Cl H 033 NH₂ Cl H 034 NH(CH₂CH₃) Cl H 035 N(CH₂C≡CH)₂ Cl H 036N(CH₃)(CH₂CH═CH₂) Cl H 037 NH(CH₂C₆H₅) Cl H 038

Cl H 039 NHCOCH₃ Cl H 040 NHCOCH₂CH₃ Cl H 041 NHCOCHClCH₃ Cl H 042NHCOCH₂Cl CJ H 043 NHCOCHCl₂ Cl H 044 N(CH₃)COCHCl₂ Cl H 045N(CH₂C≡CH)COCHCl₂ Cl H 046 NHCOCF₃ Cl H 047 N(COCF₃)₂ Cl H 048NHCOCF₂CF₃ Cl H 049 NHCOCClF₂ Cl H 050 NHCOCF₂CF₂CF₃ Cl H 051NHCO(2-thienyl) Cl H 052 NHCO(3-furanyl) Cl H 053NHCO(3-tetrahydrofuranyl) Cl H 054 NHCO(2-furanyl) Cl H 055NHCO(2-tetrahydrofuranyl) Cl H 056 NHSO₂CH₃ Cl H 057 N(SO₂CH₃)₂ Cl H 058NHSO₂CH₂CH₃ Cl H 059 N(CH₂C≡CH)SO₂CH₂CH₃ Cl H 060 NHSO₂CF₃ Cl H 061 ClCH₃ H 062 Br CH₃ H 063 NH₂ CH₃ H 064 NH(CH₂CH₃) CH₃ H 065 N(CH₂C≡CH)₂CH₃ H 066 N(CH₃)(CH₂CH═CH₂) CH₃ H 067 NH(CH₂C₆H₅) CH₃ H 068

CH₃ H 069 NHCOCH₃ CH₃ H 070 NHCOCH₂CH₃ CH₃ H 071 NHCOCHClCH₃ CH₃ H 072NHCOCH₂Cl CH₃ H 073 NHCOCHCl₂ CH₃ H 074 N(CH₃)COCHCl₂ CH₃ H 075N(CH₂C≡CH)COCHCl₂ CH₃ H 076 NHCOCF₃ CH₃ H 077 N(COCF₃)₂ CH₃ H 078NHCOCF₂CF₃ CH₃ H 079 NHCOCClF₂ CH₃ H 080 NHCOCF₂CF₂CF₃ CH₃ H 081NHCO(2-thienyl) CH₃ H 082 NHCO(3-furanyl) CH₃ H 083NHCO(3-tetrahydrofuranyl) CH₃ H 084 NHCO(2-furanyl) CH₃ H 085NHCO(2-tetrahydrofuranyl) CH₃ H 086 NHSO₂CH₃ CH₃ H 087 N(SO₂CH₃)₂ CH₃ H088 NHSO₂CH₂CH₃ CH₃ H 089 N(CH₂C≡CH)SO₂CH₂CH₃ CH₃ H 090 NHSO₂CF₃ CH₃ H091 Cl F H 092 Br F H 093 NH₂ F H 094 NH(CH₂CH₃) F H 095 N(CH₂C≡CH)₂ F H096 N(CH₃)(CH₂CH═CH₂) F H 097 NH(CH₂C₆H₅) F H 098

F H 099 NHCOCH₃ F H 100 NHCOCH₂CH₃ F H 101 NHCOCHClCH₃ F H 102 NHCOCH₂ClF H 103 NHCOCHCl₂ F H 104 N(CH₃)COCHCl₂ F H 105 N(CH₂C≡CH)COCHCl₂ F H106 NHCOCF₃ F H 107 N(COCF₃)₂ F H 108 NHCOCF₂CF₃ F H 109 NHCOCClF₂ F H110 NHCOCF₂CF₂CF₃ F H 111 NHCO(2-thienyl) F H 112 NHCO(3-furanyl) F H113 NHCO(3-tetrahydrofuranyl) F H 114 NHCO(2-furanyl) F H 115NHCO(2-tetrahydrofuranyl) F H 116 NHSO₂CH₃ F H 117 N(SO₂CH₃)₂ F H 118NHSO₂CH₂CH₃ F H 119 N(CH₂CCH)SO₂CH₂CH₃ F H 120 NHSO₂CF₃ F H 121 Cl Cl F122 Br Cl F 123 NH₂ Cl F 124 NH(CH₂CH₃) Cl F 125 N(CH₂C≡CH)₂ Cl F 126N(CH₃)(CH₂CH═CH₂) Cl F 127 NH(CH₂C₆H₅) Cl F 128

Cl F 129 NHCOCH₃ Cl F 130 NHCOCH₂CH₃ Cl F 131 NHCOCHClCH₃ Cl F 132NHCOCH₂Cl Cl F 133 NHCOCHCl₂ Cl F 134 N(CH₃)COCHCl₂ Cl F 135N(CH₂C≡CH)COCHCl₂ Cl F 138 NHCOCF₃ Cl F 137 N(COCF₃)₂ Cl F 138NHCOCF₂CF₃ Cl F 139 NHCOCClF₂ Cl F 140 NHCOCF₂CF₂CF₃ Cl F 141NHCO(2-thienyl) Cl F 142 NHCO(3-furanyl) Cl F 143NHCO(3-tetrahydrofuranyl) Cl F 144 NHCO(2-furanyl) Cl F 145NHCO(2-tetrahydrofuranyl) Cl F 146 NHSO₂CH₃ Cl F 147 N(SO₂CH₃)₂ Cl F 148NHSO₂CH₂CH₃ Cl F 149 N(CH₂C≡CH)SO₂CH₂CH₃ C1 F 150 NHSO₂CF₃ Cl F 151 ClBr H 152 Br Br H 153 NH₂ Br H 154 NH(CH₂CH₃) Br H 155 N(CH₂C≡CH)₂ Br H156 N(CH₃)(CH₂CH═CH₂) Br H 157 NH(CH₂C₆H₅) Br H 158

Br H 159 NHCOCH₃ Br H 160 NHCOCH₂CH₃ Br H 161 NHCOCHClCH₃ Br H 162NHCOCH₂Cl Br H 163 NHCOCHCl₂ Br H 164 N(CH₃)COCHCl₂ Br H 165N(CH₂C≡CH)COCHCl₂ Br 166 NHCOCF₃ Br H 167 N(COCF₃)₂ Br H 168 NHCOCF₂CF₃Br H 169 NHCOCClF₂ Br H 170 NHCOCF₂CF₂CF₃ Br H 171 NHCO(2-thienyl) Br H172 NHCO(3-furanyl) Br H 173 NHCO(3-tetrahydrofuranyl) Br H 174NHCO(2-furanyl) Br H 175 NHCO(2-tetrahydrofuranyl) Br H 176 NHSO₂CH₃ BrH 177 N(SO₂CH₃)₂ Br H 178 NHSO₂CH₂CH₃ Br H 179 N(CH₂C≡CH)SO₂CH₂CH₃ Br H180 NHSO₂CF₃ Br H 181 NH₂ Cl Cl 182 NHCOCHCl₂ Cl Cl 163 NHCOCH₂Cl Cl Cl184 NH₂ F Cl 185 NHCOCHCl₂ F Cl

TABLE 3 Compounds of the formulae I₆₈-I₁₀₆, I₁₃₇-I₁₄₆

Comp. No. I_(n) n = 68-106, 137-146 R₁₁ R₁₃ 001 F F 002 F H 003 F Cl 004F NH₂ 005 F OH 006 F SH 007 F Br 008 F I 009 F CN 010 F SO₂Cl 011 FNH(CH₃) 012 F N(CH₂CH₃)₂ 013 F NH(COCH₃) 014 F N(SO₂CH₃)₂ 015 FNH(SO₂CH₂CH₃) 016 F N(CH₂CH═CH₂)(SO₂CH₂CH₃) 017 FN(CH₂C≡CH)(SO₂CH(CH₃)₂) 018 F OCH₃ 019 F OCH₂CH₃ 020 F OCH(CH₃)₂ 021 FOCH₂CHCH₂ 022 F OCH(CH₃)CH═CH₂ 023 F OCH₂C≡CH 024 F OCH(cyclopentyl) 025F OCH₂(2-F—C₆H₅) 026 F OCH(CH₃)(4-CH₃—C₆H₅) 027 F OC₆H₅ 028 F OCH₂CH₂Cl029 F OCH₂CH═CHCl 030 F OCH₂CH₂OH 031 F OCH₂OCH₃ 032 F OCH₂CH₂OCH₂CH₃033 F OCH₂CH₂OCH₂CH₂OCH₂CH₃ 034 F OCH(CH₃)CH₂OCH₂CH═CH₂ 035 F OCOCH₃ 036F OCOOCH₃ 037 F OCOCH₂C₆H₅ 038 F OCH₂SCH₃ 039 F OCH₂COOH 040 FOCH(CH₃)COOH 041 F OCH₂COOCH₂CH₃ 042 F OCH(CH₃)COOCH₃ 043 FOCH(CH₃)COOCH₂CH═CH₂ 044 F OCH(CH₃)COOCH₂(C₆H₅) 045 F OCH(CH₃)CH₂COOH046 F OCH(CH₃)CH₂COOCH₂CH₃ 047 F OCH(CH₃)COSCH₂CH₃ 048 F OCH₂CONH₂ 049 FOCH₂CON(CH₂CH₃)₂ 050 F OCH(CH₃)CON(CH₃)₂ 051 F OCH(CH₃)CONH(CH₂CH═CH₂)052 F OCH(CH₃)CON(CH₃)(CH₂C≡CH) 053 F OCH(CH₃)CON(CH₃)(C₆H₅) 054 FOCH₂COOCH₂CH₂SCH₃ 055 F OCH(CH(CH₃)₂)COOH 056 F OCH(CH₃)COOCH₂CH₂OCH₂CH₃057 F OCH(C₆H₅)COOH 058 F OCH(C₆H₅)COOCH₃ 059 F OCH(C₆H₅)COOCH(CH₃)C≡CH060 F OCH(C₆H₅)COOCH₂C₆H₅ 061 F OCH(C₆H₅)COSCH(CH₃)₂ 062 FOCH(C₆H₅)CONH₂ 063 F OCH(C₆H₅)CONH(CH₂C≡CH) 064 FOCH(C₆H₅)CON(CH₂CH═CH₂)₂ 065 F OCH(C₆H₅)CON(CH₃)CH₂C₆H₅ 066 FOCH(C₆H₅)CONH(cyclopropyl) 067 F OCH₂CH₂COOH 068 F OCH₂CH₂COOCH₂CH₃ 069F OCH(CH₃)CH₂COOH 070 F SCH₃ 071 F SCH(CH₃)₂ 072 F SCH₂CH═CH₂ 073 FSCH₂C₆H₅ 074 F SCH₂CH₂OCH₃ 075 F SCH₂COOH 076 F SCH₂COOCH₂C₆H₅ 077 FSCH(CH₃)COOH 078 F SCH(CH₃)COOCH₂CH₃ 079 F SCH(CH₃)COOCH₂CH═CH₂ 080 FSCH(CH₃)CON(CH₃)₂ 081 F SCH(CH₃)CONH(CH₂CH═CH₂) 082 F SOCH₂CH₃ 083 FSO₂CH₃ 084 F SO₂NH₂ 085 F SO₂N(CH₃)₂ 086 F SO₂N(CH₂CH₃)₂ 087 FSO₂N(CH₃)(CH₂(4-CH₃—C₆H₅)) 088 F SO₂NHCH₂CH₂OCH₃ 089 F SCOOCH₃ 090 FSCON(CH₃)₂ 091 F SCONHCH₂CH═CH₂ 092 F SCOOCH₂CH═CH₂ 093 FSCON(CH₂CH₃)COCF₃ 094 F CHO 095 F COCH₃ 096 F COOCH₂CH₃ 097 F COOCH₂C₆H₅098 F COCl 099 F COCH₂CH₂Cl 100 F COOH 101 F COOCH₃ 102 F COOCH₂CH₃ 103F COOCH(CH₃)₂ 104 F COOCH₂CH═CH₂ 105 F COO(CH₂)5CH₃ 106 FCOOCH(CH₃)CH═CH₂ 107 F COOCH₂CH₂OCH₂CH₃ 108 F COOCH(CH₃)CH₂SCH₃ 109 FCOOCH₂(oxiranyl) 110 F COO(cylopentyl) 111 F COSCH₃ 112 F COSCH(CH₃)₂113 F COSCH₂C₆H₅ 114 F CONH₂ 115 F CONH(CH₂CH═CH₂) 116 F CONHCH₂C₆H₅ 117F CON(CH₂CH═CH₂)₂ 118 F CON(CH₃)OCH₃ 119 F COOCH₂CH₂COOH 120 FCOOCH(CH₃)COOCH₃ 121 F COOCH(CH₃)COOCH₂C₆H₅ 122 F COOCH(CH₃)CH₂COOCH₂CH₃123 F COOCH(CH₃)CH₂CONHCH₂CH₃ 124 F COOCH(CH₃)CH₂CON(CH₃)₂ 125 FCOOCH(CH₃)CH₂COSCH₂CH₃ 126 F COOCH(CH₃)CH₂COOCH₂CH═CH₂ 127 FCOOC(CH₃)₂COCH₃ 128 F COOC(CH₃)₂COOH 129 F COOC(CH₃)₂COOCH₃ 130 FCOOC(CH₃)₂COOCH₂CH₃ 131 F COOC(CH₃)₂COOCH(CH₃)₂ 132 FCOOC(CH₃)COO(CH₂)₄CH₃ 133 F COOC(CH₃)₂COOCH₂C₆H₅ 134 FCOOC(CH₃)₂COOCH₂(2-F—C₆H₅) 135 F COOC(CH₃)₂COOCH₂CH═CH₂ 136 FCOOC(CH₃)₂COOCH(CH₃)CH═CH₂ 137 F COOC(CH₃)₂COOCH₂C≡CH 138 FCOO(CH₃)₂COOCH₂CH₂OCH₂CH₃ 139 F COOC(CH₃)₂COSCH₃ 140 FCOOC(CH₃)₂COSCH(CH₃)₂ 141 F COOC(CH₃)₂COSCH₂C₆H₅ 142 F COOC(CH₃)₂CONH₂143 F COOC(CH₃)₂CONHCH₂CH═CH₂ 144 F COOC(CH₃)₂CON(CH₂CH₃)₂ 145 FCOOC(CH₃)₂CON(CH₃)CH₂CH₂OCH₃ 146 F COSCH(CH₃)COOH 147 F COSCH(CH₃)COOCH₃148 F COSCH(CH₃)CONHCH₂CH═CH₂ 149 F CON(CH₃)CH₂COOH 150 FCON(CH₃)C(CH₃)₂COOCH₂CH₃ 151 F CON(CH₃)OCH₂COOCH₃ 152 F CON(CH₃)OH 153 FCH₃ 154 F CH₂CH₃ 155 F CH(OH)CH₃ 156 F CH(OCH₂CH═CH₂)CH₃ 157 F CH₂Cl 158F CH₂OH 159 F CH₂OCOCH₃ 160 F CHClCH₃ 161 F CH₂CH₂CF₃ 162 F CH═CHCF₃ 163F CH₂CH═CH₂ 164 F CH═CHCH₃ 165 F C≡CH 166 F C≡CCH₂OH 167 F CH₂CHClCOOH168 F (R)—CH₂CHClCOOH 169 F (S)—CH₂CHClCOOH 170 F CH₂CH(CH₃)COOH 171 FCH₂CH(CH₃)COOCH₂CH₃ 172 F CH(Cl)CH₂COOCH₃ 173 F CH(Cl)C(Cl)₂COOH 174 FCH(Cl)CH(Cl)COOCH₂CH₃ 175 F CH₂CH(CH₃)COOH 176 F CH₂CH(CH₃)COCH₂CH═CH₂177 F CH₂CH(CH₃)CONH(CH₂CH═CH₂) 178 F CH₂CH(CH₃)CON(CH₃)₂ 179 FCH₂CH(CH₃)COSCH(CH₃)₂ 180 F CH₂CHClCOOC(CH₃)₃ 181 F CH₂CHClCOOCH₃ 182 FCH₂CHClCOOCH₂CH₃ 183 F CH₂CHClCOOCH(CH₃)₂ 184 F CH₂CHClCOOCH₂CH═CH₂ 185F CH₂CHClCOOCH₂C₆H₅ 186 F CH₂CHClCOSCH(CH₃)₂ 187 F CH₂CHClCOSCH₂C₆H₅ 188F CH₂CHClCONH₂ 189 F CH₂CHClCONH(CH₂CH═CH₂) 190 F CH₂CHClCON(CH₂CH₃)₂191 F CH₂CHClCONH(CH₂C₆H₅) 192 F CH₂CHClCON(CH₃)CH₂C₆H₅ 193 F CH═CHCOOH194 F (E)-CH═CHCOOH 195 F (Z)-CH═CHCOOH 196 F CH═CHCOOCH₃ 197 FCH═CHCOOCH₂C₆H₅ 198 F CH═CHCOONH₂ 199 F CH═CHCONH(CH₂CH═CH₂) 200 FCH═C(Cl)COOH 201 F CH═C(Cl)CONH₂ 202 F CH═C(Cl)CONH(CH₂CH₃) 203 FCH═C(Cl)CON(CH₂CH₃)₂ 204 F CH═C(Cl)CONH(CH₂C₆H₅) 205 F CH═C(Cl)COSCH₃206 F CH═C(Cl)COSCH(CH₃)₂ 207 F CH═C(CH₃)COOH 208 FCH═C(CH₃)CONH(CH₂CH═CH₂) 209 F CH═C(CH₃)CON(CH₃)₂ 210 FCH═C(CH₃)COSCH₂CH₃ 211 F CH═C(CN)COOH 212 F CH═C(CN)COOC(CH₃)₃ 213 FCH═C(CN)CON(CH₂CH═CH₂)₂ 214 F CH═C(COOH)₂ 215 F CH═C(C₆H₅)COOH 216 FCH═CHCH₂OH 217 Cl F 218 Cl H 219 Cl Cl 220 Cl NH₂ 221 Cl OH 222 Cl SH223 Cl Br 224 Cl I 225 Cl CN 226 Cl SO₂Cl 227 Cl NH(CH₃) 228 ClN(CH₂CH₃)₂ 229 Cl NH(COCH₃) 230 Cl NH(CH₂CH═CH₂) 231 Cl N(CH₃)(CH₂C≡CH)232 Cl N(SO₂CH₃)₂ 233 Cl NH(SO₂CH₂CH₃) 234 Cl N(CH₂CH═CH₂)(SO₂CH₂CH₃)235 Cl N(CH₂C≡CH)(SO₂CH(CH₃)₂) 236 Cl N(CH₂CF₃)(CHO) 237 Cl NH(CH₂C₆H₅)238 Cl OCH₃ 239 Cl OCH₂CH₃ 240 Cl OCH(CH₃)₂ 241 Cl OCH(CH₃)CH₂CH₂CH₃ 242Cl OCH₂CH═CH₂ 243 Cl OCH(CH₃)CH═CH₂ 244 Cl OCH₂C≡CH 245 Cl OCH(CH₃)C≡CH246 Cl OCH(cyclopentyl) 247 Cl OCH₂(C₆H₅) 248 Cl OCH₂(2-F—C₆H₅) 249 ClOCH(CH₃)(4-CH₃—C₆H₅) 250 Cl OC₆H₅ 251 Cl O(4-pyrimidyl) 252 Cl OCH₂CH₂Cl253 Cl OCH₂CH═CHCl 254 Cl OCH₂CH₂OH 255 Cl OCH₂OCH₃ 256 ClOCH₂CH₂OCH₂CH₃ 257 Cl OCH₂CH₂OCH₂CH₂OCH₂CH₃ 258 Cl OCH(CH₃)CH₂OCH₂CH═CH₂259 Cl OCOCH₃ 260 Cl OCOOCH₃ 261 Cl OCOCH₂C₆H₅ 262 Cl OCH₂SCH₃ 263 ClOCH₂CH₂SCH₂CH₃ 264 Cl OCH₂COOH 265 Cl OCH(CH₃)COOH 266 Cl(R)—OCH(CH₃)COOH 267 Cl (S)—OCH(CH₃)COOH 268 Cl OCH₂COOCH₂CH₃ 269 ClOCH(CH₃)COOCH₃ 270 Cl OCH(CH₃)COOCH₂CH═CH₂ 271 Cl OCH(CH₃)COOCH₂(C₆H₅)272 Cl OCH(CH₃)CH₂COOH 273 Cl OCH(CH₃)CH₂COOCH₂CH₃ 274 Cl OCH₂COSCH₃ 275Cl OCH(CH₃)COSCH₂CH₃ 276 Cl OCH(CH₃)COSCH(CH₃)₂ 277 Cl OCH₂CONH₂ 278 ClOCH₂CON(CH₂CH₃)₂ 279 Cl OCH(CH₃)CON(CH₃)₂ 280 Cl OCH(CH₃)CONH(CH₂CH═CH₂)281 Cl OCH(CH₃)CON(CH₃)(CH₂C≡CH) 282 Cl OCH(CH₃)CON(CH₂C₆H₅)₂ 283 ClOCH(CH₃)CON(CH₃)(C₆H₅) 284 Cl OCH₂COOCH₂CH₂SCH₃ 285 Cl OCH(CH(CH₃)₂)COOH286 Cl OCH(CH₃)COOCH₂CH₂OCH₂CH₃ 287 Cl OCH(C₆H₅)COOH 288 Cl(R)—OCH(C₆H₅)COOH 289 Cl (S)—OCH(C₆H₅)COOH 290 Cl OCH(C₆H₅)COOCH₃ 291 ClOCH(C₆H₅)COOCH(CH₃)C≡CH 292 Cl OCH(C₆H₅)COOCH₂C₆H₅ 293 ClOCH(C₆H₅)COSCH(CH₃)₂ 294 Cl OCH(C₆H₅)CONH₂ 295 Cl OCH(C₆H₅)CONH(CH₂C≡CH)296 Cl OCH(C₆H₅)CON(CH₂CH═CH₂)₂ 297 Cl OCH(C₆H₅)CON(CH₃)CH₂C₆H₅ 298 ClOCH(C₆H₅)CONH(CH₂(2-F—C₆H₅)) 299 Cl OCH(C₆H₅)CONH(cyclopropyl) 300 ClOCH₂CH₂COOH 301 Cl OCH₂CH₂COOCH₂CH₃ 302 Cl OCH(CH₃)CH₂COOH 303 Cl SCH₃304 Cl SCH(CH₃)₂ 305 Cl SCH₂CH═CH₂ 308 Cl SCH₂C₆H₅ 307 Cl SCH₂CH₂OCH₃308 Cl SC₆H₅ 309 Cl SCH₂COOH 310 Cl SCH₂COOCH₂C₆H₅ 311 Cl SCH(CH₃)COOH312 Cl SCH(CH₃)COOCH₂CH₃ 313 Cl SCH(CH₃)COOCH₂CH═CH₂ 314 ClSCH(CH₃)COSCH₃ 315 Cl SCH(CH₃)CON(CH₃)₂ 316 Cl SCH(CH₃)CONH(CH₂CH═CH₂)317 Cl SOCH₂CH₃ 318 Cl SO₂CH₃ 319 Cl SO₂NH₂ 320 Cl SO₂N(CH₃)₂ 321 ClSO₂N(CH₂CH₃)₂ 322 Cl SO₂N(CH₃)(CH₂(4-CH₃—C₆H₅)) 323 Cl SO₂NHCH₂CH₂OCH₃324 Cl SCOOCH₃ 325 Cl SCON(CH₃)₂ 326 Cl SCONHCH₂CH═CH₂ 327 ClSCOOCH₂CH═CH₂ 328 Cl SCON(CH₂CH₃)COCF₃ 329 Cl CHO 330 Cl COCH₃ 331 ClCOOCH₂CH₃ 332 Cl COOCH₂C₆H₅ 333 Cl COCl 334 Cl COCH₂CH₂Cl 335 Cl COOH336 Cl COOCH₃ 337 Cl COOCH₂CH₃ 338 Cl COOCH(CH₃)₂ 339 Cl COOCH₂CH═CH₂340 Cl COO(CH₂)₅CH₃ 341 Cl COOCH(CH₃)CH═CH₂ 342 Cl COOCH₂(2-F—C₆H₅) 343Cl COOC₆H₅ 344 Cl COOCH₂CH₂OCH₂CH₃ 345 Cl COOCH(CH₃)CH₂SCH₃ 346 ClCOO(oxetanyl) 347 Cl COOCH₂(oxiranyl) 348 Cl COO(cylopentyl) 349 ClCOSCH₃ 350 Cl COSCH(CH₃)₂ 351 Cl COSCH₂C₆H₅ 352 Cl CONH₂ 353 ClCONH(CH₂CH═CH₂) 354 Cl CONHCH₂C₆H₅ 355 Cl CON(CH₂CH═CH₂)₂ 356 ClCON(CH₃)OCH₃ 357 Cl COOCH₂CH₂COOH 358 Cl COOCH(CH₃)COOCH₃ 359 ClCOOCH(CH₃)COOCH₂C₆H₅ 360 Cl COOCH(CH₃)CH₂COOCH₂CH₃ 361 Cl (S)—COOCH(CH₃)CH₂COOCH₂CH═CH₂ 362 Cl (R)—COOCH(CH₃)CH₂COOCH₂CH═CH₂ 363 ClCOOCH(CH₃)CH₂CONHCH₂CH₃ 364 Cl COOCH(CH₃)CH₂CON(CH₃)₂ 365 ClCOOCH(CH₃)CH₂COSCH₂CH₃ 366 Cl COOCH(CH₃)CH₂COOCH₂CH═CH₂ 367 ClCOOC(CH₃)₂COCH₃ 368 Cl COOC(CH₃)₂COOH 369 Cl COOC(CH₃)₂COOCH₃ 370 ClCOOC(CH₃)₂COOCH₂CH₃ 371 Cl COOC(CH₃)₂COOCH(CH₃)₂ 372 ClCOOC(CH₃)COO(CH₂)₄CH₃ 373 Cl COOC(CH₃)₂COOCH₂C₆H₅ 374 ClCOOC(CH₃)₂COOCH₂(2-F—C₆H₅) 375 Cl COOC(CH₃)₂COOCH₂CH═CH₂ 376 ClCOOC(CH₃)₂COOCH(CH₃)CH═CH₂ 377 Cl COOC(CH₃)₂COOCH₂C≡CH 378 ClCOO(CH₃)₂COOCH₂CH₂OCH₂CH₃ 379 Cl COOC(CH₃)₂COSCH₃ 380 ClCOOC(CH₃)₂COSCH(CH₃)₂ 381 Cl COOC(CH₃)₂COSCH₂C₆H₅ 382 Cl COOC(CH₃)₂CONH₂383 Cl COOC(CH₃)₂CONHCH₂CH═CH₂ 384 Cl COOC(CH₃)₂CON(CH₂CH₃)₂ 385 ClCOOC(CH₃)₂CON(CH₃)CH₂CH₂OCH₃ 386 Cl COSCH(CH₃)COOH 387 ClCOSCH(CH₃)COOCH₃ 388 Cl COSCH(CH₃)CONHCH₂CH═CH₂ 389 Cl CON(CH₃)CH₂COOH390 Cl CON(CH₃)C(CH₃)₂COOCH₂CH₃ 391 Cl CON(CH₃)OCH₂COOCH₃ 392 ClCON(CH₃)OH 393 Cl CH₃ 394 Cl CH₂CH₃ 395 Cl CH(OH)CH₃ 396 ClCH(OCH₂CH═CH₂)CH₃ 397 Cl CH₂Cl 398 Cl CH₂OH 399 Cl CH₂OCOCH₃ 400 ClCHClCH₃ 401 Cl CH₂CH₂CF₃ 402 Cl CH═CHCF₃ 403 Cl CH₂CH═CH₂ 404 ClCH═CH(CH₃) 405 Cl C≡CH 406 Cl C≡CCH₂OH 407 Cl CH₂CHClCOOH 408 Cl(R)—CH₂CHClCOOH 409 Cl (S)—CH₂CHClCOOH 410 Cl CH₂CH(CH₃)COOH 411 ClCH₂CH(CH₃)COOCH₂CH₃ 412 Cl CH(Cl)CH₂COOCH₃ 413 Cl CH(Cl)C(Cl)₂COOH 414Cl CH(Cl)CH(Cl)COOCH₂CH₃ 415 Cl CH₂CH(CH₃)COOH 416 ClCH₂CH(CH₃)COCH₂CH═CH₂ 417 Cl CH₂CH(CH₃)CONH(CH₂CH═CH₂) 418 ClCH₂CH(CH₃)CON(CH₃)₂ 419 Cl CH₂CH(CH₃)COSCH(CH₃)₂ 420 ClCH₂CHClCOOC(CH₃)₃ 421 Cl CH₂CHClCOOCH₃ 422 Cl CH₂CHClCOOCH₂CH₃ 423 ClCH₂CHClCOOCH(CH₃)₂ 424 Cl CH₂CHClCOOCH₂CH═CH₂ 425 Cl CH₂CHClCOOCH₂C₆H₅426 Cl CH₂CHClCOSCH₃ 427 Cl CH₂CHClCOSCH(CH₃)₂ 428 Cl CH₂CHClCOSCH₂C₆H₅429 Cl CH₂CHClCONH₂ 430 Cl CH₂CHClCONH(CH₂CH═CH₂) 431 ClCH₂CHClCON(CH₂CH₃)₂ 432 Cl CH₂CHClCONH(CH₂C₆H₅) 433 ClCH₂CHClCON(CH₃)CH₂C₆H₅ 434 Cl CH═CHCOOH 435 Cl (E)-CH═CHCOOH 436 Cl(Z)-CH═CHCOOH 437 Cl CH═CHCOOCH₃ 438 Cl CH═CHCOOCH₂C₆H₅ 439 ClCH═CHCOONH₂ 440 Cl CH═CHCONH(CH₂CH═CH₂) 441 Cl CH═C(Cl)COOH 442 ClCH═C(Cl)CONH₂ 443 Cl CH═C(Cl)CONH(CH₂CH₃) 444 Cl CH═C(Cl)CON(CH₂CH₃)₂445 Cl CH═C(Cl)CONH(CH₂C₆H₅) 446 Cl CH═C(Cl)COSCH₃ 447 ClCH═C(Cl)COSCH(CH₃) 448 Cl CH═C(CH₃)COOH 449 Cl CH═C(CH₃)CONH(CH₂CH═CH₂)450 Cl CH═C(CH₃)CON(CH₃)₂ 451 Cl CH═C(CH₃)COSCH₂CH₃ 452 Cl CH═C(CN)COOH453 Cl CH═C(CN)COOC(CH₃)₃ 454 Cl CH═C(CN)CON(CH₂CH═CH₂)₂ 455 ClCH═C(COOH)₂ 456 Cl CH═C(C₆H₅)COOH 457 Cl CH═CHCH₂OH 458 H F 459 H H 460H Cl 461 H Br 462 H I 463 H NH₂ 464 H OH 465 H SH 466 H SO₂Cl 467 H CN468 H NH(CH₂C₆H₅) 469 H N(CH₂CH═CH₂)₂ 470 H N(SO₂CH₃)₂ 471 HNH(SO₂CH₂CH₃ 472 H NH(COCH₃) 473 H OCH₃ 474 H OCH₂CH₃ 475 H OCH₂CH═CH₂476 H OCH₂C≡CH 477 H OCH₂C₆H₅ 478 H OCH₂CH₂Cl 479 H OCH₂CH₂OH 480 HOCH₂OCH₃ 481 H OCH₂CH₂OCH₂CH₃ 482 H OCH₂CH₂OCH₂CH₂OCH₃ 483 H OCOCH₃ 484H OCOOCH₃ 485 H OCH₂SCH₃ 486 H OCH₂CH₂SCH₃ 487 H OCH₂COOH 488 HOCH₂COOCH₃ 489 H OCH₂COOCH₂C₆H₅ 490 H OCH₂CONH(CH₃) 491 H OCH(CH₃)COOH492 H OCH(CH₃)COOCH₂CH₃ 493 H OCH(CH₃)COOCH₂CH═CH₂ 494 HOCH(CH₃)COOCH₂C₆H₅ 495 H OCH(CH₃)CONH₂ 496 H OCH(CH₃)CONH(CH₂CH═CH₂) 497H OCH(CH₃)CON(CH₃)₂ 498 H OCH(CH₃)COSCH(CH₃)₂ 499 H OCH(C₆H₅)COOH 500 HOCH(C₆H₅)COOCH₃ 501 H OCH(C₆H₅)COOCH₂CH═CH₂ 502 H OCH(C₆H₅)CONH₂ 503 HOCH(C₆H₅)CONH(CH₂CH₃) 504 H OCH(C₆H₅)CON(CH₃)₂ 505 H OCH(C₆H₅)COSCH₃ 508H OCH(C₆H₅)COSCH(CH₃)₂ 507 H OCH(CH₃)CH₂COOH 508 H OCH(CH₃)CH₂COOCH₂CH₃509 H SCH₃ 510 H SCH(CH₃)₂ 511 H SCH₂C₆H₅ 512 H SCH(CH₃)COOH 513 HSCH(CH₃)COOCH₂CH₃ 514 H SO₂NH₂ 515 H SO₂NH(CH₂CH═CH₂) 516 H SO₂N(CH₃)₂517 H SCOCH₃ 518 H SCOOCH₂CH₃ 519 H CHOCOCH₃ 520 H COOH 521 H COCl 522 HCOOCH₃ 523 H COOCH(CH₃)₂ 524 H COOCH₂C₆H₅ 525 H COSCH(CH₃)₂ 526 H CONH₂527 H CONHCH₂C₆H₅ 528 H CON(CH₂CH═CH₂)₂ 529 H CON(CH₃)OCH₃ 530 HCOOCH(CH₃)CH₂COOH 531 H COOCH(CH₃)COOCH₂CH₃ 532 HCOOCH(CH₃)CH₂COOCH₂CH═CH₂ 533 H COOCH(CH₃)CH₂COSCH₂CH₃ 534 HCOOCH(CH₃)CH₂CONH₂ 535 H COOCH(CH₃)CH₂CONH(CH₂CH═CH₂) 536 HCOOCH(CH₃)COOH 537 H COOC(CH₃)₂COOH 538 H COOC(CH₃)₂COOCH₃ 539 HCOOC(CH₃)₂COOCH(CH₃)₂ 540 H COOC(CH₃)₂COOCH₂CH₃ 541 HCOOC(CH₃)₂COOCH₂CH═CH₂ 542 H COOC(CH₃)₂COOCH₂CH₂OCH₂CH₃ 543 HCOOC(CH₃)₂CONH₂ 544 H COOC(CH₃)₂CON(CH₃)₂ 545 HCOOC(CH₃)₂CONH(CH₂CH═CH₂) 546 H COSCH(CH₃)COOH 547 H CON(CH₃)C(CH₃)₂COOH548 H CH₃ 549 H CH₂CH₃ 550 H CH(OH)CH₃ 551 H CH₂Cl 552 H CH₂OH 553 HCH₂OCOCH₃ 554 H CH═CHCF₃ 555 H CH₂CH₂CF₃ 556 H CH₂CHCH₂ 557 HCH₂CHClCOOH 558 H CH₂CHClCOOCH₂CH₃ 559 H CH₂CHClCOOCH₂C₆H₅ 560 HCH₂CHClCOOCH₂CH═CH₂ 561 H CH₂CHClCOOC(CH₃)₃ 562 H CH₂CHClCOSCH(CH₃)₂ 563H CH₂CHClCONH₂ 564 H CH₂CHClCONH(CH₂CH₃) 565 H CH₂CHClCON(CH₃)₂ 566 HCH(Cl)CH(Cl)COOH 567 H CH₂C(CH₃)ClCOOH 568 H CH₂C(CH₃)ClCOOCH₂CH₃ 569 HCH₂C(CH₃)ClCOSCH₃ 570 H CH₂C(CH₃)ClCONH(CH₂CH═CH₂) 571 HCH₂C(CH₃)ClCON(CH₃)(CH₂CH═CH₂) 572 H CH═CHCOOH 573 H CH═C(CH₃)COOH 574 HCH═C(Cl)COOH 575 H CH═C(CN)COOH 576 H CH═C(CN)COOCH₂CH═CH₂ 577 HCH═C(Cl)COOCH₂CH₃ 578 H CH═C(CH₃)CONH(CH₂CH═CH₂) 579 H CH═C(Cl)COSCH₂CH₃580 H CH═C(Cl)CON(CH₃)₂ 581 CH₃ F 582 CH₃ H 583 CH₃ Cl 584 CH₃ Br 585CH₃ I 586 CH₃ NH₂ 587 CH₃ OH 588 CH₃ SH 589 CH₃ SO₂Cl 590 CH₃ CN 591 CH₃NH(CH₂C₆H₅) 592 CH₃ N(CH₂CH═CH₂)₂ 593 CH₃ N(SO₂CH₃)₂ 594 CH₃NH(SO₂CH₂CH₃ 595 CH₃ NH(COCH₃) 596 CH₃ OCH₃ 597 CH₃ OCH₂CH₃ 598 CH₃OCH₂CH═CH₂ 599 CH₃ OCH₂C≡CH 600 CH₃ OCH₂C₆H₅ 601 CH₃ OCH₂CH₂Cl 602 CH₃OCH₂CH₂OH 603 CH₃ OCH₂OCH₃ 604 CH₃ OCH₂CH₂OCH₂CH₃ 605 CH₃OCH₂CH₂OCH₂CH₂OCH₃ 606 CH₃ OCOCH₃ 607 CH₃ OCOOCH₃ 608 CH₃ OCH₂SCH₃ 609CH₃ OCH₂CH₂SCH₃ 610 CH₃ OCH₂COOH 611 CH₃ OCH₂COOCH₃ 612 CH₃OCH₂COOCH₂C₆H₅ 613 CH₃ OCH₂CONH(CH₃) 614 CH₃ OCH(CH₃)COOH 615 CH₃OCH(CH₃)COOCH₂CH₃ 616 CH₃ OCH(CH₃)COOCH₂CH═CH₂ 617 CH₃OCH(CH₃)COOCH₂C₆H₅ 618 CH₃ OCH(CH₃)CONH₂ 619 CH₃ OCH(CH₃)CONH(CH₂CH═CH₂)620 CH₃ OCH(CH₃)CON(CH₃)₂ 621 CH₃ OCH(CH₃)COSCH(CH₃)₂ 622 CH₃OCH(C₆H₅)COOH 623 CH₃ OCH(C₆H₅)COOCH₃ 624 CH₃ OCH(C₆H₅)COOCH₂CH═CH₂ 625CH₃ OCH(C₆H₅)CONH₂ 626 CH₃ OCH(C₆H₅)CONH(CH₂CH₃) 627 CH₃OCH(C₆H₅)CON(CH₃)₂ 628 CH₃ OCH(C₆H₅)COSCH₃ 629 CH₃ OCH(C₆H₅)COSCH(CH₃)₂630 CH₃ OCH(CH₃)CH₂COOH 631 CH₃ OCH(CH₃)CH₂COOCH₂CH₃ 632 CH₃ SCH₃ 633CH₃ SCH(CH₃)₂ 634 CH₃ SCH₂C₆H₅ 635 CH₃ SCH(CH₃)COOH 636 CH₃SCH(CH₃)COOCH₂CH₃ 637 CH₃ SO₂NH₂ 638 CH₃ SO₂NH(CH₂CH═CH₂) 639 CH₃SO₂N(CH₃)₂ 640 CH₃ SCOCH₃ 641 CH₃ SCOOCH₂CH₃ 642 CH₃ CHOCOCH₃ 643 CH₃COOH 644 CH₃ COCl 645 CH₃ COOCH₃ 646 CH₃ COOCH(CH₃)₂ 647 CH₃ COOCH₂C₆H₅648 CH₃ COSCH(CH₃)₂ 649 CH₃ CONH₂ 650 CH₃ CONHCH₂C₆H₅ 651 CH₃CON(CH₂CH═CH₂)₂ 652 CH₃ CON(CH₃)OCH₃ 653 CH₃ COOCH(CH₃)CH₂COOH 654 CH₃COOCH(CH₃)COOCH₂CH₃ 655 CH₃ COOCH(CH₃)CH₂COOCH₂CH═CH₂ 656 CH₃COOCH(CH₃)CH₂COSCH₂CH₃ 657 CH₃ COOCH(CH₃)CH₂CONH₂ 658 CH₃COOCH(CH₃)CH₂CONH(CH₂CH═CH₂) 659 CH₃ COOCH(CH₃)COOH 660 CH₃COOC(CH₃)₂COOH 661 CH₃ COOC(CH₃)₂COOCH₃ 662 CH₃ COOC(CH₃)₂COOCH(CH₃)₂663 CH₃ COOC(CH₃)₂COOCH₂CH₃ 664 CH₃ COOC(CH₃)₂COOCH₂CH═CH₂ 665 CH₃COOC(CH₃)₂COOCH₂CH₂OCH₂CH₃ 666 CH₃ COOC(CH₃)₂CONH₂ 667 CH₃COOC(CH₃)₂CON(CH₃)₂ 668 CH₃ COOC(CH₃)₂CONH(CH₂CH═CH₂) 669 CH₃COSCH(CH₃)COOH 670 CH₃ CON(CH₃)C(CH₃)₂COOH 671 CH₃ CH₃ 672 CH₃ CH₂CH₃673 CH₃ CH(OH)CH₃ 674 CH₃ CH₂Cl 675 CH₃ CH₂OH 676 CH₃ CH₂OCOCH₃ 677 CH₃CH═CHCF₃ 678 CH₃ CH₂CH₂CF₃ 679 CH₃ CH₂CH═CH₂ 680 CH₃ CH₂CHClCOOH 681 CH₃CH₂CHClCOOCH₂CH₃ 682 CH₃ CH₂CHClCOOCH₂C₆H₅ 683 CH₃ CH₂CHClCOOCH₂CH═CH₂684 CH₃ CH₂CHClCOOC(CH₃)₃ 685 CH₃ CH₂CHClCOSCH(CH₃)₂ 686 CH₃CH₂CHClCONH₂ 687 CH₃ CH₂CHClCONH(CH₂CH₃) 688 CH₃ CH₂CHClCON(CH₃)₂ 689CH₃ CH(Cl)CH(Cl)COOH 690 CH₃ CH₂C(CH₃)ClCOOH 691 CH₃CH₂C(CH₃)ClCOOCH₂CH₃ 692 CH₃ CH₂C(CH₃)ClCOSCH₃ 693 CH₃CH₂C(CH₃)ClCONH(CH₂CH═CH₂) 694 CH₃ CH₂C(CH₃)ClCON(CH₃)(CH₂CH═CH₂) 695CH₃ CH═CHCOOH 696 CH₃ CH═C(CH₃)COOH 697 CH₃ CH═C(Cl)COOH 698 CH₃CH═C(CN)COOCH₂CH═CH₂ 699 CH₃ CH═C(CN)COOH 700 CH₃ CH═C(Cl)COOCH₂CH₃ 701CH₃ CH═C(CH₃)CONH(CH₂CH═CH₂) 702 CH₃ CH═C(Cl)COSCH₂CH₃ 703 CH₃CH═C(Cl)CON(CH₃)₂

TABLE 4 Compounds of the formulae I₁₀₇-I₁₃₆, I₁₄₉-I₁₅₆, II₁-II₁₃,III₁-III₉, IV₁, IV₂, V₁ and V₂

(III₁),

(III₂),

(III₃),

(III₄),

(III₅),

(III₆),

(III₇),

(III₈),

(III₉),

(IV₁),

(IV₂),

(V₁),

(V₂),

(I₁₀₇),

(I₁₀₈),

(I₁₀₉),

(I₁₁₀),

(I₁₁₁),

(I₁₁₂),

(I₁₁₃),

(I₁₁₄),

(I₁₁₅),

(I₁₁₆),

(I₁₁₇),

(I₁₁₈),

(I₁₁₉),

(I₁₂₀),

(I₁₂₁),

(I₁₂₂),

(I₁₂₃),

(I₁₂₄),

(I₁₂₅),

(II₁),

(II₂),

(II₃),

(II₄),

(II₅),

(II₆),

(II₇),

(II₈),

(II₉),

(II₁₀),

(II₁₁),

(II₁₂),

(II₁₃),

(I₁₂₆),

(I₁₂₇),

(I₁₂₈),

(I₁₂₉),

(I₁₃₀),

(I₁₃₁),

(I₁₃₂),

(I₁₃₃),

(I₁₃₄),

(I₁₃₅),

(I₁₃₆),

(I₁₄₉),

(I₁₅₀),

(I₁₅₁),

(I₁₅₂),

(I₁₅₃),

(I₁₅₄),

(I₁₅₅),

(I₁₅₆), Comp. No. I₁₀₇-I₁₃₆; I₁₄₉-I₁₅₆; II₁-II₁₃; III₁-III₉; IV₁, IV₂;V₁, V₂ R₁₁ R₁₂ R₁₃ 001 H Cl H 002 H Cl CH₃ 003 H Cl COOH 004 H Cl COOCH₃005 H Cl COOCH₂CH₃ 006 H Cl COOCH₂C₆H₅ 007 H Cl OH 008 H Cl OCH₃ 009 HCl OCH₂C₆H₅ 010 H Cl OCH₂COOH 011 H Cl F 012 H Cl Cl 013 H Cl Br 014 HCl NH₂ 015 H Cl NHCOCH₃ 016 H Cl SH 017 H Cl SCH₃ 018 H Br H 019 H BrCH₃ 020 H Br COOH 021 H Br COOCH₃ 022 H Br COOCH₂CH₃ 023 H Br COOCH₂C₆H₅024 H Br OH 025 H Br OCH₃ 026 H Br OCH₂C₆H₅ 027 H Br OCH₂COOH 028 H Br F029 H Br Cl 030 H Br Br 031 H Br NH₂ 032 H Br NHCOCH₃ 033 H Br SH 034 HBr SCH₃ 035 F Cl H 036 F Cl CH₃ 037 F Cl COOH 038 F Cl COOCH₃ 039 F ClCOOCH₂CH₃ 040 F Cl COOCH₂C₆H₅ 041 F Cl OH 042 F Cl OCH₃ 043 F ClOCH₂C₆H₅ 044 F Cl OCH₂COOH 045 F Cl F 046 F Cl Cl 047 F Cl Br 048 F ClNH₂ 049 F Cl NHCOCH₃ 050 F Cl SH 051 F Cl SCH₃ 052 Cl Cl H 053 Cl Cl CH₃054 Cl Cl COOH 055 Cl Cl COOCH₃ 056 Cl Cl COOCH₂CH₃ 057 Cl Cl COOCH₂C₆H₅058 Cl Cl OH 059 Cl Cl OCH₃ 060 Cl Cl OCH₂C₆H₅ 061 Cl Cl OCH₂COOH 062 ClCl F 063 Cl Cl Cl 064 Cl Cl Br 065 Cl Cl NH₂ 066 Cl Cl NHCOCH₃ 067 Cl ClSH 068 Cl Cl SCH₃ 069 F Br H 070 F Br CH₃ 071 F Br COOH 072 F Br COOCH₃073 F Br COOCH₂CH₃ 074 F Br COOCH₂C₆H₅ 075 F Br OH 076 F Br OCH₃ 077 FBr OCH₂C₆H₅ 078 F Br OCH₂COOH 079 F Br F 080 F Br Cl 081 F Br Br 082 FBr NH₂ 083 F Br NHCOCH₃ 084 F Br SH 085 F Br SCH₃ 086 F CH₃ H 087 F CH₃CH₃ 088 F CH₃ COOH 089 F CH₃ COOCH₃ 090 F CH₃ COOCH₂CH₃ 091 F CH₃COOCH₂C₆H₅ 092 F CH₃ OH 093 F CH₃ OCH₃ 094 F CH₃ OCH₂C₆H₅ 095 F CH₃OCH₂COOH 096 F CH₃ F 097 F CH₃ Cl 098 F CH₃ Br 099 F CH₃ NH₂ 100 F CH₃NHCOCH₃ 101 F CH₃ SH 102 F CH₃ SCH₃ 103 Cl CF₃ H 104 Cl CF₃ CH₃ 105 ClCF₃ COOH 106 Cl CF₃ COOCH₃ 107 Cl CF₃ COOCH₂CH₃ 108 Cl CF₃ COOCH₂C₆H₅109 Cl CF₃ OH 110 Cl CF₃ OCH₃ 111 Cl CF₃ OCH₂C₆H₅ 112 Cl CF₃ OCH₂COOH113 Cl CF₃ F 114 Cl CF₃ Cl 115 Cl CF₃ Br 116 Cl CF₃ NH₂ 117 Cl CF₃NHCOCH₃ 118 Cl CF₃ SH 119 Cl CF₃ SCH₃ 120 Cl CHF₂ H 121 Cl CHF₂ CH₃ 122Cl CHF₂ COOH 123 Cl CHF₂ COOCH₃ 124 Cl CHF₂ COOCH₂CH₃ 125 Cl CHF₂COOCH₂C₆H₅ 126 Cl CHF₂ OH 127 Cl CHF₂ OCH₃ 128 Cl CHF₂ OCH₂C₆H₅ 129 ClCHF₂ OCH₂COOH 130 Cl CHF₂ F 131 Cl CHF₂ Cl 132 Cl CHF₂ Br 133 Cl CHF₂NH₂ 134 Cl CHF₂ NHCOCH₃ 135 Cl CHF₂ SH 136 Cl CHF₂ SCH₃ 137 Cl CH₃ H 138Cl CH₃ CH₃ 139 Cl CH₃ COOH 140 Cl CH₃ COOCH₃ 141 Cl CH₃ COOCH₂CH₃ 142 ClCH₃ COOCH₂C₆H₅ 143 Cl CH₃ OH 144 Cl CH₃ OCH₃ 145 Cl CH₃ OCH₂C₆H₅ 146 ClCH₃ OCH₂COOH 147 Cl CH₃ F 148 Cl CH₃ Cl 149 Cl CH₃ Br 150 Cl CH₃ NH₂ 151Cl CH₃ NHCOCH₃ 152 Cl CH₃ SH 153 Cl CH₃ SCH₃ 154 Cl CHO H 155 Cl CHO CH₃156 Cl CHO COOH 157 Cl CHO COOCH₃ 158 Cl CHO COOCH₂CH₃ 159 Cl CHOCOOCH₂C₆H₅ 160 Cl CHO OH 161 Cl CHO OCH₃ 162 Cl CHO OCH₂C₆H₅ 163 Cl CHOOCH₂COOH 164 Cl CHO F 165 Cl CHO Cl 166 Cl CHO Br 167 Cl CHO NH₂ 168 ClCHO NHCOCH₃ 169 Cl CHO SH 170 Cl CHO SCH₃ 171 F CHO H 172 F CHO CH₃ 173F CHO COOH 174 F CHO COOCH₃ 175 F CHO COOCH₂CH₃ 176 F CHO COOCH₂C₆H₅ 177F CHO OH 178 F CHO OCH₃ 179 F CHO OCH₂C₆H₅ 180 F CHO OCH₂COOH 181 F CHOF 182 F CHO Cl 183 F CHO Br 184 F CHO NH₂ 185 F CHO NHCOCH₃ 186 F CHO SH187 F CHO SCH₃

TABLE 5 Compounds prepared, from the preceding Tables 1-4, withphysico-chemical data. Comp.No. Physico-chemical data I₁.002 Meltingpoint 95-96° C. I₁.003 Melting point 63-67° C. I₁.005 Melting point126-128° C. I₁.007 Melting point 76-77° C. I₁.009 Melting point 133-134°C. I₁.022 Melting point 149-150° C. I₁.023 Melting point 82-83° C.I₁.024 Melting point 80-81° C. I₁.026 Solid I₁.028 Melting point122-123° C. I₁.031 Melting point 71-75° C. I₁.046 Melting point 78-79°C. I₁.088 Melting point 63-64° C. I₁.113 Melting point 120-121° C.I₁.114 Melting point 114-115° C. I₁.115 Melting point 82-85° C. I₁.119Solid I₁.120 Melting point 83-84° C. I₁.121 ¹H-NMR (CDCl₃): 7.70 ppm (d,1H); 6.73 ppm (t, 1H); 4.48 ppm (q, 2H); 3.89 ppm (s, 3H); 1.43 ppm (t,3H); solid I₁.122 Resin I₁.132 Resin I₁.134 Melting point 108-110° C.I₁.154 Amorphous I₁.157 Resin I₁.159 Melting point 79-81° C. I₁.164Melting point 81-82° C. I₁.168 Solid I₁.177 Melting point 94-95° C.I₁.190 Melting point 92-94° C. I₁.243 Melting point 88-89° C. I₁.393Melting point 133-134° C. I₁.735 Meltng point 81-84° C. I₁.736 Meltingpoint 74-76° C. I₁.737 Solid I₁.738 Melting point 76-79° C. I₁.739 ResinI₁.740 Melting point 75-77° C. I₁.741 Melting point 115-116° C. I₁.742Solid I₁.743 Solid I₁.744 Solid I₁.745 Melting point 79-80° C. I₁.746Melting point 83-84° C. I₁.747 Melting point 138-139° C. I₁.748 Meltingpoint 76-77° C. I₁.749 Melting point 147-149° C. I₁.750 Melting point57-62° C. I₁.751 Resin I₁.752 Resin I₁.753 Melting point 134-136° C.I₁.754 Resin I₁.755 Melting point 42-44° C. I₁.756 Melting point115-116° C. I₁.757 Melting point 57-59° C. I₁.758 Resin I₁.759 ResinI₁.760 Resin I₁.761 Melting point 83-84° C. I₁.764 Isomer A: resin;isomer B: melting point 89-91° C. I₁.805 Amorphous I₁.806 Melting point84-88° C. I₁.807 Melting point 84-86° C. I₁.808 Melting point 108-109°C. I₄.002 Melting point 76-78° C. I₄.022 Solid I₄.028 Melting point98-101° C. I₄.121 Melting point 82-83° C. I₄.243 Resin I₄.484 SolidI₄.485 Solid I₄.498 Solid I₄.566 Solid I₄.570 Solid I₄.729 Solid I₄.733Solid I₆.002 Melting point 80-81° C. I₆.028 Melting point 108-110° C.I₆.121 Melting point 88-89° C. I₉.002 Melting point 130-132° C. I₉.121Melting point 137-140° C. I₁₀.002 Melting point 144-146° C. I₁₈.002Melting point 61-64° C. I₁₈.243 Oil I₁₉.002 Melting point 112-114° C.I₁₉.243 Melting point 92-93° C. I₂₀.002 Melting point 145-147° C.I₂₀.243 Melting point 120-135° C. I₃₀.002 Oil I₃₀.243 Melting point49-53° C. I₃₁.243 Melting point 105-108° C. I₃₂.002 Melting point154-157° C. I₃₂.243 Melting point 107-112° C. I₆₃.001 Solid I₆₈.002Melting point 115-117° C. I₆₈.003 Melting point 114-118° C. I₇₀.153Melting point 85-89° C. I₇₁.002 Melting point 81-83° C. I₇₁.023 Meltingpoint 108-110° C. I₇₃.002 Melting point 56-58° C. I₇₃.023 Melting point100-102° C. I₇₅.002 Melting point 159-161° C. I₇₅.473 Solid I₇₆.002Solid I₉₇.002 Melting point 174-176° C. I₁₀₃.002 Melting point 79-80° C.I₁₀₄.002 Melting point 111-116° C. I₁₀₅.002 Melting point 77-79° C.I₁₀₆.002 Melting point 96-97° C. I₁₀₇.035 Melting point 86-88° C.I₁₀₈.035 Solid I₁₀₈.052 Melting point 148-152° C. I₁₀₉.035 Melting point83-85° C. I₁₁₀.035 Melting point 161-163° C. I₁₁₀.052 Solid I₁₁₅.035Melting point 92-94° C. I₁₂₈.035 Melting point 84-86° C. I₁₂₉.103 ResinI₁₂₉.052 Melting point 104-105° C. I₁₃₀.035 Melting point 194-196° C.I₁₃₁.035 Melting point 110-111° C. I₁₃₂.035 Melting point 72-73° C.I₁₃₃.035 Solid I₁₃₄.035 Melting point 92-94° C. I₁₃₅.035 Melting point77-78° C. I₁₃₆.035 Melting point 108-109° C. I₁₃₇.002 Melting point80-82° C. I₁₃₈.002 Melting point 47-49° C. I₁₃₉.002 Melting point118-122° C. I₁₄₄.002 Melting point 132-133° C. I₁₄₅.002 Melting point83-84° C. I₁₄₆.002 Melting point 95-96° C. I₁₄₇.101 Melting point153-154° C. II₅.035 Melting point 99-100° C. II₁₀.035 Melting point201-204° C. II₁₃.035 Melting point 117-118° C. III₁.035 TLC analysis(silica gel 60 F₂₅₄; n-hexane/AcOEt/AcOH 20/20/1: Rf-value 0.59 III₁.052TLC analysis (silica gel 60 F₂₅₄; n-hexane/AcOEt/AcOH 20/20/1: Rf-value0.67 III₄.001 TLC analysis (silica gel 60 F₂₅₄; n-hexane/AcOEt/AcOH40/20/1: Rf-value 0.33 III₄.103 TLC analysis (silica gel 60 F₂₅₄;n-hexane/AcOEt/AcOH 20/20/1: Rf-value 0.47

Formulation examples for active substances of the formula I (%=per centbv weight

F1. Emulsion concentrates a) b) c) d) Active substance according 5% 10%25% 50% to Tables 1-4 Calcium dodecylbenzene- 6%  8%  6%  8% sulfonateCastor oil polyglycol ether 4% —  4%  4% (36 mol of EO) Octylphenolpolyglycol ether —  4% —  2% (7-8 mol of EO) Cyclohexanone — — 10% 20%Aromatic hydrocarbon 85%  78% 55% 16% mixture C₉-C₁₂

Emulsions of any desired concentration can be preprepared from suchconcentrates by dilution with water.

F2. Solutions a) b) c) d) Active substance  5% 10% 25% 50% according toTables 1-4 1-Methoxy-3-(3-methoxy- — 20% 20% — propoxy)propanePolyethylene glycol 20% 10% — — molecular weight 400N-Methyl-2-pyrrolidone — — 30% 10% Aromatic hydrocarbon 75% 60% — —mixture C₉-C₁₂

The solutions are suitable for use in the form of tiny drops.

F3. Wettable powders a) b) c) d) Active substance according 5% 25%  50% 80% to Tables 1-4 Sodium ligninsulfonate 4% — 3% — Sodium lauryl sulfate2% 3% — 4% Sodium diisobutyl-naphthalene- — 6% 5% 6% sulfonateOctytphenol polyglycol ether — 1% 2% — (7-8 mol of EO) Highly dispersesilicic acid 1% 3% 5% 10% Kaolin 88%  62%  35%  —

The active substance is mixed thoroughly with the additives and themixture is ground thoroughly in a suitable mill. Wettable powders whichcan be diluted with water to give suspensions of any desiredconcentration are obtained.

F4. Coated granules a) b) c) Active subtance according 0.1% 5% 15% toTables 1-4 Highly disperse silicic acid 0.9% 2%  2% Inorganic carriermaterial 9.0% 93%  83% (Ø 0.1-1 mm), for example CaCO₃ or SiO₂

The active substance is dissolved in methylene chloride, the solution issprayed onto the carrier and the solvent is then evaporated off invacuo.

F5. Coated granules a) b) c) Active substance according to 0.1% 5% 15%Tables 1-4 Polyethylene glycol 1.0% 2%  3% molecular weight 200 Highlydisperse silicic acid 0.9% 1%  2% Inorganic carrier material 98.0%  92% 80% (Ø 0.1-1 mm) for example CaCO₃ or SiO₂

The finely ground active substance is applied uniformly to the carriermaterial, which has been moistened with polyethylene glycol, in a mixer.Dust-free coated granules are obtained in this manner.

F6. Extruded granules a) b) c) d) Active substance according to 0.1% 3%5% 15% Tables 1-4 Sodium ligninsulfonate 1.5% 2% 3%  4%Carboxymethylcellulose 1.4% 2%  2% Kaolin 97.0%  93%  90%  79%

The active substance is mixed with the additives and the mixture isground and moistened with water. This mixture is extruded and then driedin a stream of air.

F7. Dusts a) b) c) Active substance according to  0.1%  1%  5% Tables1-4 Talc 39.9% 49% 35% Kaolin 60.0% 50% 60%

Ready-to use dusts are obtained by mixing the active substance with thecarriers and grinding the mixture on a suitable mill.

F8. Suspension concentrates a) b) c) d) Active substance according to 3%10%  25%  50%  Tables 1-4 Ethylene glycol 5% 5% 5% 5% Nonylphenolpolyglycol ether — 1% 2% — (15 mol of EO) Sodium ligninsulfonate 3% 3%4% 5% Carboxymethylcellulose 1% 1% 1% 1% 37% aqueous formaldehyde 0.2%  0.2%   0.2%   0.2%   solution Silicone oil emulsion 0.8%   0.8%   0.8%  0.8%   Water 87%  79%  62%  38% 

The finely ground active substance is mixed intimately with theadditives. A suspension concentrate from which suspensions of anydesired concentration can be prepared by dilution with water is thusobtained.

BIOLOGICAL EXAMPLES Example B1

Herbicidal action before emergence of the plants (pre-emergence action)

Monocotyledon and dicotyledon test plants are sown in standard soil inplastic pots. Immediately after sowing, the test substances are sprayedon (500 l of water/ha) as an aqueous suspension or emulsion preparedfrom a 25% emulsion concentrate (Example F1, c)), corresponding to adosage of 2000 g of AS/ha. The test plants are then grown under optimumconditions in a greenhouse. After a test period of 3 weeks, the test isevaluated with a 9-level scale of ratings (1=complete damage, 9=noaction). Ratings of 1 to 4 (in particular 1 to 3) mean a good to verygood herbicidal action.

Test plants: Setaria, Solanum

The compounds according to the invention show a good herbicidal action.

Table B1 gives examples of the good herbicidal activity of the compoundsof the formual I.

TABLE B1 Pre-emergence action: Dose Test plants: Setaria Solanum [g ofAS/ha] Active substance No. I₁.002 1 1 2000 I₁.003 1 1 500 I₁.005 2 12000 I₁.007 1 1 2000 I₁.009 1 1 2000 I₁.022 1 1 2000 I₁.023 1 1 2000I₁.024 1 1 2000 I₁.026 1 1 2000 I₁.028 1 1 2000 I₁.031 1 1 2000 I₁.046 11 2000 I₁.088 1 1 2000 I₁.113 1 1 2000 I₁.119 1 1 2000 I₁.120 1 1 2000I₁.121 1 1 2000 I₁.122 1 1 2000 I₁.134 1 1 2000 I₁.154 1 1 2000 1₁.157 11 2000 I₁.159 1 1 2000 I₁.164 1 1 2000 I₁.168 1 1 2000 I₁.243 1 1 2000I₁.393 1 1 2000 I₁.735 1 2 2000 I₁.736 1 1 2000 I₁.737 3 1 2000 I₁.738 11 2000 I₁.739 1 1 2000 I₁.740 1 1 2000 I₁.741 1 1 2000 I₁.745 1 1 2000I₁.746 1 4 2000 I₁.747 1 1 2000 I₁.748 1 1 2000 I₁.749 5 2 2000 I₁.750 11 2000 I₄.002 1 1 2000 I₄.028 1 1 2000 I₄.121 1 1 2000 I₄.484 1 1 2000I₄.485 1 1 2000 I₄.498 2 1 2000 I₄.566 2 1 2000 I₄.570 1 1 2000 I₆.002 11 2000 I₆.028 1 1 2000 I₆.121 1 1 2000 I₉.002 1 1 2000 I₉.121 2 3 2000I₁₀.002 1 1 2000 I₂₀.002 1 1 2000 I₆₃.001 1 1 2000 I₆₈.002 1 1 2000I₆₈.003 1 1 2000 I₇₁.002 1 1 2000 I₇₃.002 1 1 2000 I₇₅.002 2 1 2000I₇₅.473 1 1 2000 I₇₆.002 1 1 2000 I₉₇.002 3 2 2000 I₁₀₃.002 1 1 2000I₁₀₅.002 2 1 2000 I₁₀₆.002 2 1 2000 I₁₃₆.035 2 3 2000 I₁₃₇.002 1 1 2000

The same results are obtained if the compounds of the formula I areformulated according to Examples F2 to F8.

Example B2

Post-emergence herbicidal action

Monocotyledon and dicotyledon test plants are grown in plastic pots withstandard soil in a greenhouse and, in the 4- to 6-leaf stage, aresprayed with an aqueous suspension or emulsion of the test substances ofthe formula 1, prepared from a 25% emulsion concentrate (Example F1,c)), corresponding to a dosage of 2000 g of AS/ha (500 l of water/ha).The test plants are then grown further under optimum conditions in agreenhouse. After a test period of about 18 days, the test is evaluatedwith a 9-level scale of rating (1=complete damage, 9=no action). Ratingsof 1 to 4 (in particular 1 to 3) mean a good to very good herbicidalaction.

Test plants: Setaria, Sinapis, Solanum, Ipomoea

The compounds of the formula I also show a potent herbicidal action inthis test.

Table B2 gives examples of the good herbicidal activity of the compoundsof the formula I.

TABLE B2 Post-emergence action: Dose Test plant: Setaria Sinapis SolanumIpomoea [g of AS/ha] Active substance No. I₁.002 1 1 1 1 2000 I₁.003 2 11 1 500 I₁.005 1 1 1 1 2000 I₁.007 1 1 1 1 2000 I₁.009 5 1 1 1 2000I₁.022 3 1 1 1 2000 I₁.023 1 1 1 1 2000 I₁.024 2 1 1 1 2000 I₁.026 1 1 11 2000 I₁.028 1 1 1 1 2000 I₁.031 3 1 1 1 2000 I₁.046 1 1 1 1 2000I₁.088 1 1 1 1 2000 I₁.113 1 1 1 1 2000 I₁.119 1 1 1 1 2000 I₁.120 1 1 11 2000 I₁.121 1 1 1 1 2000 I₁.122 1 1 1 1 2000 I₁.134 1 1 1 1 2000I₁.154 1 1 1 1 2000 I₁.157 1 1 1 1 2000 I₁.159 2 1 1 1 2000 I₁.164 1 1 11 2000 I₁.168 2 1 1 1 2000 I₁.243 1 1 1 1 2000 I₁.393 1 1 1 1 2000I₁.735 3 2 1 1 2000 I₁.736 1 1 1 1 2000 I₁.737 2 1 1 1 2000 I₁.738 1 1 11 2000 I₁.739 1 1 1 1 2000 I₁.740 1 1 1 1 2000 I₁.741 1 1 1 1 2000I₁.742 1 1 1 1 2000 I₁.743 1 1 1 1 2000 I₁.744 1 1 1 1 2000 I₁.745 4 1 11 2000 I₁.746 3 2 1 1 2000 I₁.747 1 1 1 1 2000 I₁.748 3 1 1 1 2000I₁.749 5 2 1 1 2000 I₁.750 1 1 1 1 2000 I₄.002 6 5 1 1 2000 I₄.028 2 1 11 2000 I₄.121 1 1 1 1 2000 I₄.484 4 6 1 1 2000 I₄.485 6 2 1 2 2000I₄.570 3 4 1 1 2000 I₆.002 6 3 1 1 2000 I₆.028 3 1 1 1 2000 I₆.121 1 1 11 2000 I₉.002 2 3 1 1 2000 I₉.121 3 3 1 1 2000 I₁₀.002 5 6 1 1 2000I₂₀.002 4 2 1 1 2000 I₆₃.001 3 1 1 1 2000 I₆₈.002 1 1 1 1 2000 I₆₈.003 21 1 1 2000 I₇₁.002 1 1 1 1 2000 I₇₃.002 1 4 1 1 2000 I₇₅.002 6 3 2 12000 I₇₅.473 5 4 1 2 2000 I₉₇.002 5 2 1 1 2000 I₁₀₃.002 6 5 1 3 2000I₁₀₅.002 6 5 1 1 2000 I₁₀₆.002 3 2 1 1 2000 I₁₃₇.002 4 1 1 1 2000

The same results are obtained if the compounds of the formula I areformulated according to Examples F2 to F8.

What is claimed is:
 1. A compound of the formula I

in which A is ═N— or

n₁₃ is 1, 2 or 3; R₁ is hydrogen, C₁-C₄alkyl, C₁-C₄halogenoalkyl,cyano-C₁-C₄alkyl, C₃- or C₄alkenyl, C₃- or C₄halogenoalkenyl, C₃- orC₄alkynyl or C₃-C₆cycloalkyl; R₂ is C₁-C₄halogenoalkyl; R₃ is hydrogen,C₁-C₄alkyl, C₁-C₄halogenoalkyl, C₁-C₄hydroxyalkyl, C₂-C₆alkenyl,C₂-C₆-halogenoalkenyl, C₂-C₆alkynyl, halogen, cyano, NH₂C(S)—, nitro,OHC— or R₁₈R₁₉N—; R₁₈ and R₁₉ independently of one another are hydrogen,C₁-C₄alkyl, C₁-C₄halogenoalkyl, C₃-C₄alkenyl, C₃-C₄halogenoalkenyl,C₃-C₆cycloalkyl, C₃-C₆alkynyl, C₁-C₆alkylcarbonyl,C₁-C₆halogenoalkylcarbonyl, C₂-C₆alkenylcarbonyl,C₂-C₆halogenoalkenylcarbonyl, C₁-C₆alkylsulfonyl orC₁-C₆halogenoalkylsulfonyl; R₁₁ is hydrogen, fluorine, chlorine, bromineor methyl; R₁₃ is hydrogen, halogen, cyano, CIS(O)₂—, CIC(O)—, nitro,amino,

HS—, R₂₀NH— or R₂₀R₂₁ N—; R₂₀ and R₂₁ independently of one another areC₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₃-C₆cycloalkyl,C₁-C₈halogenoalkyl, C₃-C₈halogenoalkenyl, C₁-C₄alkylcarbonyl,C₁-C₄-halogenoalkylcarbonyl, C₁-C₄alkylsulfonyl,C₁-C₄halogenalkylsulfonyl, benzyl or benzyl which is substituted on thephenyl ring once to three times by halogen, C₁-C₄alkyl orC₁-C₄-halogenoalkyl; or R₁₃ is R₃₀O—; R₃₀ is hydrogen, C₁-C₈alkyl,C₃-C₈alkenyl, C₃-C₈alkynyl, C₃-C₆cycloalkyl, C₁-C₈-halogenoalkyl,C₃-C₈halogenoalkenyl, C₁-C₄alkoxy-C₁-C₄alkyl,C₃-C₆alkenyloxy-C₁-C₄alkyl, C₃-C₆alkynyloxy-C₁-C₄alkyl,C₁-C₄alkoxy-C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl,C₁-C₈alkoxycarbonyl, C₃-C₈alkenyloxycarbonyl, benzyloxycarbonyl, phenyl,benzyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, where thesearomatic and heteroaromatic rings mentioned can be unsubstituted orsubstituted once to three times by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl; or R₃₀ is R₃₁X₁C(O)—C₁-C₈alkyl- or

X₁ is oxygen, sulfur or

R₃₁ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₃-C₆cycloalkyl, C₁-C₈-halogenoalkyl, C₃-C₈halogenoalkenyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆alkenyloxy-C₁-C₄alkyl,C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenyl which is substituted once tothree times by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl, benzyl orbenzyl which is substituted once to three times on the phenyl ring byhalogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl; R₃₂ is hydrogen, C₁-C₈alkyl,C₃-C₈alkenyl, C₃-C₈alkynyl, C₃-C₆cycloalkyl or C₁-C₈-halogenoalkyl; orR₁₃ is R₃₃S(O)_(n2)—; n₂ is 0, 1 or 2; R₃₃ is C₁-C₈alkyl, C₃-C₈alkenyl,C₃-C₈alkynyl, C₃-C₆cyCloalkyl, C₁-C₈halogenoalkyl, C₃-C₈halogenoalkenyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆alkenyloxy-C₁-C₄alkyl,C₁-C₄alkylthio-C₁-C₄-alkyl, phenyl, phenyl which is substituted once tothree times by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl, benzyl orbenzyl which is substituted once to three times on the phenyl ring byhalogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl, and, if n₂ is 0, R₃₃ ishydrogen, C₁-C₈alkylcarbonyl or R₃₄X₂C(O)—; X₂ is oxygen, sulfur or

R₃₄ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₃-C₆cycloalkyl, C₁-C₈-halogenoalkyl, C₃-C₈halogenoalkenyl,C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆alkenyloxy-C₁-C₄alkyl,C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenyl which is substituted once tothree times by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl, benzyl orbenzyl which is substituted once to three times on the phenyl ring byhalogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl; R₃₅ is hydrogen, C₁-C₈alkylor C₃-C₈alkenyl; or R₁₃ is R₃₆R₃₇NS(O)₂—; R₃₆ is hydrogen, C₁-C₈alkyl,C₂-C₈alkenyl, C₃-C₈alkynyl or C₃-C₆cycloalkyl; R₃₇ is hydrogen,C₁-C₈alkyl, C₃-C₈alkenyl, C₃-CBalkynyl, C₁-C₈halogenoalkyl,C₁-C₄-alkylcarbonyl, C₁-C₄halogenoalkylcarbonyl, benzoyl or benzoylwhich is substituted once to three times on the phenyl ring by halogen,C₁-C₄alkyl or C₁-C₄halogenoalkyl; R₁₃ is R₄₀C(O)—; R₄₀ is hydrogen,fluorine, chlorine, C₁-C₈alkyl, C₂-C₈alkenyl, C₂-C₈alkynyl,C₃-C₆cycloalkyl, C₁-C₈halogenoalkyl, cyano-C₁-C₄alkyl,C₂-C₈halogenoalkenyl, C₁-C₄alkoxy-C₁-C₄alkyl,C₃-C₆alkenyloxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenylwhich is substituted once to three times by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl, benzyl or benzyl which is substituted once to threetimes on the phenyl ring by halogen, C₁-C₄alkyl or C₁-C₄-halogeno-alkyl;or R₁₃ is R₅₀X₃C(O)—; X₃ is oxygen, sulfur,

R₅₀ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₃-C₆cycloalkyl, C₁-C₈-halogenoalkyl, C₃-C₈halogenoalkenyl,cyano-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆alkenyloxy-C₁-C₄alkyl,(oxiranyl)—CH₂—, oxetanyl-, C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenylwhich is substituted once to three times by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl, benzyl or benzyl which is substituted once to threetimes on the phenyl ring by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl,phenyl-C₂-C₆alkyl, C₁-C₆alkyl-CO—C₁-C₄alkyl,

R₅₃X₄C(O)—C₁—C₆alkyl,

or R₅₃X₄C(O)—C₃-C₆cycloalkyl; X₄ is oxygen, sulfur,

R₅₃ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₃-C₆cycloalkyl, C₁-C₈-halogenoalkyl, C₃-C₈halogenoalkenyl,cyano-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆-alkenyloxy-C₁-C₄alkyl,(oxiranyl)—CH₂—, oxetanyl-, C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenylwhich is substituted once to three times by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl, benzyl, benzyl which is substituted once to threetimes on the phenyl ring by halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl,or phenyl-C₂-C₆alkyl; R₅₁, R₅₂, R₅₄and R₅₅ independently of one anotherare hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₁-C₈halogenoalkylor benzyl; or R₁₃ is B₁-C₁-C₈alkyl, B₁-C₂-C₈alkenyl, B₁-C₂-C₈alkynyl,B₁-C₁-C₈halogenoalkyl, B₁-C₂-C₈halogenoalkenyl,B₁-C₁-C₄alkoxy-C₁-C₄alkyl, B₁-C₁-C₄alkylthio-C₁-C₄alkyl orB₁-C₃-C₆cycloalkyl; B₁ is hydrogen, cyano, hydroxyl, C₁-C₈alkoxy,C₃-C₈alkenyloxy, R₆₀X₅C(O)—, C₁-C₄-alkylcarbonyl orC₁-C₄halogenoalkylcarbonyl; X₅ has the meaning of X₄; R₆₀ has themeaning of R₅₃ ; or R₁₃ is B₂-C(R₇₀)═CH—; B₂ is nitro, cyano orR₇₁X₆C(O)—; R₇₀ is cyano or R₇₂X₇C(O)—; X₆ and X₇ have the meaning ofX₄; and R₇₁ and R₇₂ have the meaning of R₅₃, or a pyrazole N-oxide,agrochemically tolerated salt or stereoisomer of this compound of theformula I.
 2. A compound of the formula I according to claim 1, in whichR₃ is hydrogen, C₁-C₄alkyl, C₁-C₄halogenoalkyl, C₂-Cralkenyl,C₂-C₆halogenoalkenyl, C₂-C₆alkynyl, halogen, cyano, NH₂C(S)—, nitro orR₁₈R₁₉N—.
 3. A compound of the formula I according to claim 1, which hasthe formula Ia

in which R₁, R₂, R₃, R₁₁, and R₁₃ are as defined in claim 1; and R₁₂ ishydrogen, halogen, C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl,C₁-C₄halogenoalkyl, C₂-C₄-halogenoalkenyl, nitro, amino, CHO,C₁-C₄halogenoalkoxy, cyano, C₃-C₆cycloalkyl, phenoxy, phenoxy which issubstituted once to three times by halogen, C₁-C₄alkyl orC₁-C₄-halogenoalkyl, benzyloxy or benzyloxy which is substituted once tothree times on the phenyl ring by halogen, C₁-C₄alkyl orC₁-C₄halogenoalkyl.
 4. A compound according to claim 3, in which R₃ ismethyl, C₁-C₄halogenoalkyl, chlorine or bromine.
 5. A compound accordingto claim 4, in which R₁ is C₁-C₄alkyl; R₂ is C₁- or C₂halogenoalkyl; R₃is chlorine or bromine; A is ═N—; R₁₁ is fluorine, chlorine or bromine;R₁₂ is halogen; and R₁₃ is hydrogen.
 6. A compound according to claim 5,in which R₁ is methyl or ethyl; R₂ is halogenomethyl; R₃ is chlorine;R₁, is fluorine; and R₁₂ is chlorine.
 7. A compound according to claim6, in which R₁ is methyl; and R₂ is difluoromethyl.
 8. A process for thepreparation of a compound of the formula I

in which R₁, R₂, R₁, R₁₃, A and n₁₃ are as defined in claim 1, and R₃ ishydrogen, halogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl, which comprisesreacting a compound of the formula X

in which R₁₁, R₁₃ and n₁₃ are as defined, in an alcohol of the formulaXV R₈—OH  (XV), in which R₈ is C₁-C₄alkyl, in the presence of a suitablepalladium or nickel catalyst and a base under an increased pressure ofcarbon monoxide to give the compound of the formula XI

in which R₈, R₁₁, R₁₃ and n₁₃ are as defined, hydrolysing this underacid or basic conditions to give the corresponding carboxylic acid ofthe formula XII

and converting this with a carboxylic acid halogenating reagent into thecorresponding carboxylic acid halide of the formula XIII

in which R₁₁, R₁₃ and n₁₃ are as defined; and Hal is halogen, andreacting this in a solvent in the presence of an alkaline earth metalsalt and a base with the malonic acid monoester salt of the formula XVI

in which R₃ is hydrogen, C₁-C₄alkyl or C₁-C₄halogenoalkyl; M₁ ⁺ is analkali metal ion and R₇ is C₁-C₄alkoxy, to give the keto ester of theformula III

in which R₃, R₇, R₁₁, R₁₃ and n₁₃ are as defined, and cyclizing this ina solvent with the compound of the formula XIV NH₂NH—R₁  (XIV), in whichR₁ is as defined in claim 1, to give the compound of the formula Ic

in which R₁, R₃, R₁₁, R₁₃ and n₁₃ are as defined, and then,functionalizing the hydroxyl group, according to the definition of R₂,if appropriate halogenating the pyrazole ring (R₃ halogen), or oxidizingthe compound to the corresponding pyridine N-oxide.
 9. A herbicidal andplant growth-inhibiting composition which comprises a herbicidallyactive content of a compound of the formula I according to claim 1 andan inert carrier.
 10. A composition according to claim 9, whichcomprises between 0.1% and 95% of an active substance of the formula I.11. A method of controlling undesirable plant growth, which comprisesapplying an active substance of the formula I according to claim 1, or acomposition comprising this active substance, to the crops of usefulplants or their environment in a herbicidally active amount.
 12. Amethod according to claim 11, wherein an amount of active substance ofbetween 0.001 and 4 kg per hectare is applied.
 13. A method ofinhibiting plant growth, which comprises applying an active substance ofthe formula I, according to claim 1 or a composition comprising thisactive substance, to the plants or their environment in an activeamount.
 14. A method according to claim 13, wherein the crops of usefulplants are cereals, maize, rice, cotton, soya, oilseed rape, sorghum,sugarcane, sugarbeet, sunflowers, vegetables, plantations and fodderplants.